Electroactive materials

ABSTRACT

A compound having Formula I, Formula II, or Formula III: 
                         
Ar 1  may independently be phenylene, substituted phenylene, naphthylene, or substituted naphthylene. Ar 2  is the same or different at each occurrence and is an aryl group. M is the same or different at each occurrence and is a conjugated moiety. T 1  and T 2  are independently the same or different at each occurrence and are conjugated moieties which are connected in a non-planar configuration; a and e are the same or different at each occurrence and are an integer from 1 to 6; b, c, and d are mole fractions such that b+c+d=1.0, with the proviso that c is not zero, and at least one of b and d is not zero, and when b is zero, M has at least two triarylamine units; and n is an integer greater than 1.

RELATED APPLICATION DATA

This application claims priority under 35 U.S.C. §119(e) from U.S.Provisional Application No. 60/988,951 filed on Nov. 19, 2007, which isincorporated by reference herein in its entirety.

BACKGROUND INFORMATION

1. Field of the Disclosure

The present disclosure relates to novel electroactive compounds. Thedisclosure further relates to electronic devices having at least oneactive layer comprising such an electroactive compound.

2. Description of the Related Art

In organic photoactive electronic devices, such as organic lightemitting diodes (“OLED”), that make up OLED displays, the organic activelayer is sandwiched between two electrical contact layers in an OLEDdisplay. In an OLED the organic photoactive layer emits light throughthe light-transmitting electrical contact layer upon application of avoltage across the electrical contact layers.

It is well known to use organic electroluminescent compounds as theactive component in light-emitting diodes. Simple organic molecules,conjugated polymers, and organometallic complexes have been used.Devices that use photoactive materials frequently include one or morecharge transport layers, which are positioned between a photoactive(e.g., light-emitting) layer and a contact layer (hole-injecting contactlayer). A device can contain two or more contact layers. A holetransport layer can be positioned between the photoactive layer and thehole-injecting contact layer. The hole-injecting contact layer may alsobe called the anode. An electron transport layer can be positionedbetween the photoactive layer and the electron-injecting contact layer.The electron-injecting contact layer may also be called the cathode.

There is a continuing need for charge transport materials for use inelectronic devices.

SUMMARY

There is provided a compound having Formula I, Formula II, or FormulaIII:

wherein:

-   -   Ar¹ is the same or different at each occurrence and is selected        from the group consisting of phenylene, substituted phenylene,        naphthylene, and substituted naphthylene;    -   Ar² is the same or different at each occurrence and is an aryl        group;    -   M is the same or different at each occurrence and is a        conjugated moiety;    -   T¹ and T² are independently the same or different at each        occurrence and are conjugated moieties which are connected in a        non-planar configuration;    -   a is the same or different at each occurrence and is an integer        from 1 to 6;    -   b, c, and d are mole fractions such that b+c+d=1.0, with the        proviso that c is not zero, and at least one of b and d is not        zero, and when b is zero, M comprises at least two triarylamine        units;    -   e is the same or different at each occurrence and is an integer        from 1 to 6; and    -   n is an integer greater than 1.

There is also provided an electronic device having at least one layercomprising the above compound.

The foregoing general description and the following detailed descriptionare exemplary and explanatory only and are not restrictive of theinvention, as defined in the appended claims.

BRIEF DESCRIPTION OF THE DRAWINGS

Embodiments are illustrated in the accompanying figures to improveunderstanding of concepts as presented herein.

FIG. 1 includes an illustration of one example of an organic electronicdevice.

Skilled artisans appreciate that objects in the figures are illustratedfor simplicity and clarity and have not necessarily been drawn to scale.For example, the dimensions of some of the objects in the figures may beexaggerated relative to other objects to help to improve understandingof embodiments.

DETAILED DESCRIPTION

There is provided a compound having Formula I, Formula II, or FormulaIII:

wherein:

-   -   Ar¹ is the same or different at each occurrence and is selected        from the group consisting of phenylene, substituted phenylene,        naphthylene, and substituted naphthylene;    -   Ar² is the same or different at each occurrence and is an aryl        group;    -   M is the same or different at each occurrence and is a        conjugated moiety;    -   T¹ and T² are independently the same or different at each        occurrence and are conjugated moieties which are connected in a        non-planar configuration;    -   a is the same or different at each occurrence and is an integer        from 1 to 6;    -   b, c, and d are mole fractions such that b+c+d=1.0, with the        proviso that c is not zero, and at least one of b and d is not        zero, and when b is zero, M comprises at least two triarylamine        units;    -   e is the same or different at each occurrence and is an integer        from 1 to 6; and    -   n is an integer greater than 1.

There is also provided an electronic device having at least one layercomprising the above compound.

Many aspects and embodiments have been described above and are merelyexemplary and not limiting. After reading this specification, skilledartisans appreciate that other aspects and embodiments are possiblewithout departing from the scope of the invention.

Other features and benefits of any one or more of the embodiments willbe apparent from the following detailed description, and from theclaims. The detailed description first addresses Definitions andClarification of Terms followed by the Electroactive Compound, theElectronic Device, and finally Examples.

1. Definitions and Clarification of Terms

Before addressing details of embodiments described below, some terms aredefined or clarified.

As used herein, the term “alkyl” includes branched and straight-chainsaturated aliphatic hydrocarbon groups. Unless otherwise indicated, theterm is also intended to include cyclic groups. Examples of alkyl groupsinclude methyl, ethyl, propyl, isopropyl, isobutyl, secbutyl, tertbutyl,pentyl, isopentyl, neopentyl, cyclopentyl, hexyl, cyclohexyl, isohexyland the like. The term “alkyl” further includes both substituted andunsubstituted hydrocarbon groups. In some embodiments, the alkyl groupmay be mono-, di- and tri-substituted. One example of a substitutedalkyl group is trifluoromethyl. Other substituted alkyl groups areformed from one or more of the substituents described herein. In certainembodiments alkyl groups have 1 to 20 carbon atoms. In otherembodiments, the group has 1 to 6 carbon atoms. The term is intended toinclude heteroalkyl groups. Heteroalkyl groups may have from 1-20 carbonatoms.

The term “aryl” means an aromatic carbocyclic moiety, which may be asingle ring (monocyclic) or multiple rings (bicyclic, or more) fusedtogether or linked covalently. Any suitable ring position of the arylmoiety may be covalently linked to the defined chemical structure.Examples of aryl moieties include, but are not limited to, phenyl,1-naphthyl, 2-naphthyl, dihydronaphthyl, tetrahydronaphthyl, biphenyl.anthryl, phenanthryl, fluorenyl, indanyl, biphenylenyl, acenaphthenyl,acenaphthylenyl, and the like. In some embodiments, aryl groups have 6to 60 carbon atoms; in some embodiments, 6 to 30 carbon atoms. The termis intended to include heteroaryl groups. Heteroaryl groups may havefrom 4-50 carbon atoms; in some embodiments, 4-30 carbon atoms.

The term “alkoxy” is intended to mean the group —OR, where R is alkyl.

The term “aryloxy” is intended to mean the group —OR, where R is aryl.

Unless otherwise indicated, all groups can be substituted orunsubstituted. An optionally substituted group, such as, but not limitedto, alkyl or aryl, may be substituted with one or more substituentswhich may be the same or different. Suitable substituents include D,alkyl, aryl, nitro, cyano, —N(R⁷)(R⁸), halo, hydroxy, carboxy, alkenyl,alkynyl, cycloalkyl, heteroaryl, alkoxy, aryloxy, heteroaryloxy,alkoxycarbonyl, perfluoroalkyl, perfluoroalkoxy, arylalkyl, silyl,siloxane, thioalkoxy, —S(O)₂—N(R′)(R″), —C(═O)—N(R′)(R″),(R′)(R″)N-alkyl, (R′)(R″)N-alkoxyalkyl, (R′)(R″)N-alkylaryloxyalkyl,—S(O)_(s)-aryl (where s=0-2) or —S(O)_(S)-heteroaryl (where s=0-2). EachR′ and R″ is independently an optionally substituted alkyl, cycloalkyl,or aryl group. R′ and R″, together with the nitrogen atom to which theyare bound, can form a ring system in certain embodiments. Substituentsmay also be crosslinking groups.

The term “charge transport,” when referring to a layer, material,member, or structure is intended to mean such layer, material, member,or structure facilitates migration of such charge through the thicknessof such layer, material, member, or structure with relative efficiencyand small loss of charge. Hole transport materials facilitate positivecharge; electron transport material facilitate negative charge. Althoughlight-emitting materials may also have some charge transport properties,the term “charge transport layer, material, member, or structure” is notintended to include a layer, material, member, or structure whoseprimary function is light emission.

The term “compound” is intended to mean an electrically unchargedsubstance made up of molecules that further include atoms, wherein theatoms cannot be separated from their corresponding molecules by physicalmeans without breaking chemical bonds. The term is intended to includeoligomers and polymers.

The term “crosslinkable group” or “crosslinking group” is intended tomean a group than can lead to crosslinking via thermal treatment orexposure to radiation. In some embodiments, the radiation is UV orvisible.

The term “electroactive” as it refers to a layer or a material, isintended to indicate a layer or material which electronicallyfacilitates the operation of the device. Examples of active materialsinclude, but are not limited to, materials which conduct, inject,transport, or block a charge, where the charge can be either an electronor a hole, or materials which emit radiation or exhibit a change inconcentration of electron-hole pairs when receiving radiation. Examplesof inactive materials include, but are not limited to, planarizationmaterials, insulating materials, and environmental barrier materials.

The prefix “fluoro” is intended to indicate that one or more hydrogensin a group has been replaced with fluorine.

The prefix “hetero” indicates that one or more carbon atoms has beenreplaced with a different atom. In some embodiments, the heteroatom isO, N, S, or combinations thereof.

The term “non-planar configuration” as it refers to [T¹-T²] in FormulaeI-III herein, is intended to mean that the immediately adjacent groupsin T¹ and T² are not oriented in the same plane.

The term “oxyalkyl” is intended to mean a heteroalkyl group having oneor more carbons replaced with oxygens. The term includes groups whichare linked via an oxygen.

The term “photoactive” is intended to mean to any material that exhibitselectroluminescence or photosensitivity.

The term “silyl” refers to the group R₃Si—, where R is H, D, C1-20alkyl, fluoroalkyl, or aryl. In some embodiments, one or more carbons inan R alkyl group are replaced with Si. In some embodiments, the silylgroups are (hexyl)₂Si(Me)CH₂CH₂Si(Me)₂— and [CF₃(CF₂)₆CH₂CH₂]₂SiMe-.

The term “siloxane” refers to the group (RO)₃Si—, where R is H, D, C1-20alkyl, or fluoroalkyl.

The phrase “adjacent to,” when used to refer to layers in a device, doesnot necessarily mean that one layer is immediately next to anotherlayer. On the other hand, the phrase “adjacent R groups,” is used torefer to R groups that are next to each other in a chemical formula(i.e., R groups that are on atoms joined by a bond).

As used herein, the terms “comprises,” “comprising,” “includes,”“including,” “has,” “having” or any other variation thereof, areintended to cover a non-exclusive inclusion. For example, a process,method, article, or apparatus that comprises a list of elements is notnecessarily limited to only those elements but may include otherelements not expressly listed or inherent to such process, method,article, or apparatus. Further, unless expressly stated to the contrary,“or” refers to an inclusive or and not to an exclusive or. For example,a condition A or B is satisfied by any one of the following: A is true(or present) and B is false (or not present), A is false (or notpresent) and B is true (or present), and both A and B are true (orpresent).

Also, use of “a” or “an” are employed to describe elements andcomponents described herein. This is done merely for convenience and togive a general sense of the scope of the invention. This descriptionshould be read to include one or at least one and the singular alsoincludes the plural unless it is obvious that it is meant otherwise.

Group numbers corresponding to columns within the Periodic Table of theelements use the “New Notation” convention as seen in the CRC Handbookof Chemistry and Physics, 81^(st) Edition (2000-2001).

Unless otherwise defined, all technical and scientific terms used hereinhave the same meaning as commonly understood by one of ordinary skill inthe art to which this invention belongs. Although methods and materialssimilar or equivalent to those described herein can be used in thepractice or testing of embodiments of the present invention, suitablemethods and materials are described below. All publications, patentapplications, patents, and other references mentioned herein areincorporated by reference in their entirety, unless a particular passageis cited. In case of conflict, the present specification, includingdefinitions, will control. In addition, the materials, methods, andexamples are illustrative only and not intended to be limiting.

To the extent not described herein, many details regarding specificmaterials, processing acts, and circuits are conventional and may befound in textbooks and other sources within the organic light-emittingdiode display, photodetector, photovoltaic, and semiconductive memberarts.

2. Electroactive Compound

The compound described herein has Formula I, Formula II, or Formula III:

wherein:

-   -   Ar¹ is the same or different at each occurrence and is selected        from the group consisting of phenylene, substituted phenylene,        naphthylene, and substituted naphthylene;    -   Ar² is the same or different at each occurrence and is an aryl        group;    -   M is the same or different at each occurrence and is a        conjugated moiety;    -   T¹ and T² are independently the same or different at each        occurrence and are conjugated moieties which are connected in a        non-planar configuration;    -   a is the same or different at each occurrence and is an integer        from 1 to 6;    -   b, c, and d are mole fractions such that b+c+d=1.0, with the        proviso that c is not zero, and at least one of b and d is not        zero, and when b is zero, M comprises at least two triarylamine        units;    -   e is the same or different at each occurrence and is an integer        from 1 to 6; and    -   n is an integer greater than 1.

In some embodiments, at least one Ar¹ is a substituted phenyl with asubstituent selected from the group consisting of alkyl, alkoxy, silyl,and a substituent with a crosslinking group. In some embodiments, a is1-3. In some embodiments a is 1-2. In some embodiments, a is 1. In someembodiments, e is 1-4. In some embodiments, e is 1-3. In someembodiments, e=1. In some embodiments, at least one Ar¹ has asubstituent that has a crosslinking group.

In some embodiments, Ar² has Formula a

where:

-   -   R¹ is the same or different at each occurrence and is selected        from the group consisting of alkyl, alkoxy, siloxane and silyl;    -   f is the same or different at each occurrence and is an integer        from 0-4;    -   g is an integer from 0-5; and    -   m is an integer from 1 to 5.        In some embodiments, at least one of f and g is not zero. In        some embodiments, m=1-3.

In some embodiments, Ar² is selected from the group consisting of agroup having Formula a, naphthyl, phenylnaphthyl, and naphthylphenyl. Insome embodiments, Ar² is selected from the group consisting phenyl,p-biphenyl, p-terphenyl, naphthyl, phenylnaphthyl, and naphthylphenyl.In some embodiments, Ar² is selected from the group consisting ofphenyl, biphenyl, and terphenyl.

Any of the aromatic rings in Formulae I-III may be substituted at anyposition. The substituents may be present to improve one or morephysical properties of the compound, such as solubility. In someembodiments, the substituents are selected from the group consisting ofC₁₋₁₂ alkyl groups, C₁₋₁₂ alkoxy groups and silyl groups. In someembodiments, the alkyl groups are heteroalkyl groups. In someembodiments, the alkyl groups are fluoroalkyl groups. In someembodiments, at least one Ar² has an alkyl, alkoxy or silyl substituent.The substituents may be present to provide crosslinking capability. Insome embodiments, crosslinking substituents are present on at least oneAr². In some embodiments, crosslinking substituents are present on atleast one M moiety. In some embodiments, there is at least onesubstituent which includes a crosslinkable group. Examples ofcrosslinkable groups include, but are not limited to vinyl, acrylate,perfluorovinylether, 1-benzo-3,4-cyclobutane, siloxane, cyanate groups,cyclic ethers (epoxides), cycloalkenes, and acetylenic groups.

In one embodiment, the crosslinkable group is vinyl.

The T¹-T² group introduces non-planarity into the backbone of thecompound. The moiety in T¹ that is directly linked to a moiety in T² islinked such that the T¹ moiety is oriented in a plane that is differentfrom the moiety in T² to which it is linked. Although other parts of theT¹ unit, for example, substituents, may lie in one or more differentplanes, it is the plane of the linking moiety in T¹ and the linkingmoiety in T² in the compound backbone that provide the non-planarity.Because of the non-planar T¹-T² linkage, the compounds are chiral. Ingeneral, they are formed as racemic mixtures. The compounds can also bein enantiomerically pure form. The non-planarity can be viewed as therestriction to free rotation about the T¹-T² bond. Rotation about thatbond leads to racemization. The half-life of racemization for T¹-T² isgreater than that for an unsubstituted biphenyl. In some embodiments,the half-life or racemization is 12 hours or greater at 20° C.

T¹ and T² are conjugated moieties. In some embodiments, T¹ and T² arearomatic moieties. In some embodiments, T¹ and T² are selected from thegroup consisting of phenylene, napthylene, and anthracenyl groups.

In some embodiments, [T¹-T²] is a substituted biphenylene group. Theterm “biphenylene” is intended to mean a biphenyl group having twopoints of attachment to the compound backbone. The term “biphenyl” isintended to mean a group having two phenyl units joined by a singlebond. The biphenylene group can be attached at one of the 2,3-, 4-, or5-positions and one of the 2′,3′-, 4′-, or 5′-positions. The substitutedbiphenylene group has at least one substitutent in the 2-position. Insome embodiments, the biphenylene group has substituents in at least the2- and 2′-positions.

In some embodiments, [T¹-T²] is a binaphthylene group. The term“binaphthylene” is intended to mean a binapthyl group having 2 points ofattachment to the compound backbone. The term “binaphthyl” is intendedto mean a group having two naphthalene units joined by a single bond. Insome embodiments, the binaphthylene group is a 1,1′-binaphthylene, whichis attached to the compound backbone at one of the 3-, 4-, 5-, 6, or7-positions and one of the 3′-, 4′-, 5′-, 6′, or 7′-positions. This isillustrated below, where the dashed lines represent possible points ofattachment.

In some embodiments, the binaphthylene group is a 1,2′-binaphthylenehaving at least one substituent at the 8- or 9′-position, and which isattached to the compound backbone at one of the 3-, 4-, 5-, 6, or7-positions and one of the 4′-, 5′-, 6′-, 7′, or 8′-positions. This isillustrated below, where the dashed lines represent possible points ofattachment and at least one R represents a substituent.

In some embodiments, the binaphthylene group is a 2,2′-binaphthylenehaving at least one substituent at the 8- or 9′-position, and which isattached to the compound backbone at one of the 4-, 5-, 6-, 7, or8-positions and one of the 4′-, 5′-, 6′-, 7′, or 8′-positions. This isillustrated below, where the dashed lines represent possible points ofattachment and at least one R represents a substituent.

In some embodiments, [T¹-T²] is a phenylene-naphthylene group. In someembodiments, [T¹-T²] is a phenylene-1-naphthylene group, which isattached to the compound backbone at one of the 3-, 4-, or 5-positionsin the phenylene and one of the 3-, 4-, or 5-positions of thenaphthylene. In some embodiments, [T¹-T²] is a phenylene-2-naphthylenegroup, which is attached to the compound backbone at one of the 3-, 4-,or 5-positions in the phenylene and one of the 4-, 5-, 6-, 7-, or8-positions of the naphthylene.

In some embodiments, the biphenylene, binaphthylene, andphenylene-naphthylene groups are substituted at one or more positions.

In some embodiments, [T¹-T²] is selected from one of the following:

where R is the same or different and is selected from the groupconsisting of alkyl, aryl, alkoxy, aryloxy, fluoroalkyl, fluoroaryl,fluoroaryloxy fluoroalkyloxy, oxyalkyl, alkenyl groups, silyl, siloxaneand crosslinking groups. The dashed line represents a possible point ofattachment to the compound backbone. In some embodiments, R is a C₁₋₁₀alkyl or alkoxy; in some embodiments, a C₃₋₈ branched alkyl or alkoxy.In some embodiments, the two R groups are joined together to form anon-aromatic ring.

In some embodiments, [T¹-T²] is a 1,1-binaphthylene group which isattached to the compound backbone at the 4 and 4′ positions, referred toas 4,4′-(1,1-binaphthylene). In some embodiments, the4,4′-(1,1-binaphthylene) is the only isomer present. In someembodiments, two or more isomers are present. In some embodiments, the4,4′-(1,1-binaphthylene) is present with up to 50% by weight of a secondisomer. In some embodiments, the second isomer is selected from thegroup consisting of 4,5′-(1,1-binaphthylene), 4,6′-(1,1-binaphthylene),and 4,7′-(1,1-binaphthylene).

Formula III represents a copolymer in which there is at least one Tmoiety and at least one other conjugated moiety. In some embodiments, cis at least 0.4. In some embodiments, c is in the range of 0.4 to 0.6.The copolymers can be random, alternating, or block copolymers. In someembodiments, M comprises triarylamine units. In some embodiments, M isan aromatic group. In some embodiments, M is an aromatic unit having acrosslinkable substituent. The amount of M having a crosslinkablesubstituent is generally between 4 and 20 mole percent.

Some non-limiting examples of compounds having Formula I includeCompounds A and B below.

Compound A:

Compound B:

Some non-limiting examples of compounds having Formula II includeCompounds C through M and M1 below.

Compound C

Compound D:

Compound E:

Compound F:

Compound G:

Compound H:

Compound I:

Compound J:

Compound K:

Compound L:

Compound M:Compound M1:

Some non-limiting examples of compounds having Formula III includeCompounds N through Y4 below.

Compound N:

Compound O:

Compound P:

Compound Q:

Compound R:

Compound S:

Compound T:

Compound U:

Compound V:

Compound W:

Compound X:

Compounds Y1-Y4

The new compounds can be made using any technique that will yield a C—Cor C—N bond. A variety of such techniques are known, such as Suzuki,Yamamoto, Stille, and Pd- or Ni-catalyzed C—N couplings. The compoundscan be formed into layers using solution processing techniques. The term“layer” is used interchangeably with the term “film” and refers to acoating covering a desired area. The term is not limited by size. Thearea can be as large as an entire device or as small as a specificfunctional area such as the actual visual display, or as small as asingle sub-pixel. Layers and films can be formed by any conventionaldeposition technique, including vapor deposition, liquid deposition(continuous and discontinuous techniques), and thermal transfer.Continuous deposition techniques, include but are not limited to, spincoating, gravure coating, curtain coating, dip coating, slot-diecoating, spray coating, and continuous nozzle coating. Discontinuousdeposition techniques include, but are not limited to, ink jet printing,gravure printing, and screen printing.

The new compounds described herein have can be used as hole transportmaterials, as photoactive materials, and as hosts for photoactivematerials. The new compounds have hole mobilities and HOMO/LUMO energiessimilar to efficient small molecule hole transport compounds such asN,N′-diphenyl-N,N′-bis(3-methylphenyl)-[1,1′-biphenyl]-4,4′-diamine(TPD) and N,N′-bis(naphthalen-1-yl)-N,N′-bis-(phenyl)benzidine (α-NPB).Compounds such as TPD and NPD generally must be applied using a vapordeposition technique.

3. Electronic Devices

Organic electronic devices that may benefit from having one or morelayers comprising at least one compound as described herein include, butare not limited to, (1) devices that convert electrical energy intoradiation (e.g., a light-emitting diode, light emitting diode display,or diode laser), (2) devices that detect signals through electronicsprocesses (e.g., photodetectors, photoconductive cells, photoresistors,photoswitches, phototransistors, phototubes, IR detectors), (3) devicesthat convert radiation into electrical energy, (e.g., a photovoltaicdevice or solar cell), and (4) devices that include one or moreelectronic components that include one or more organic semi-conductorlayers (e.g., a transistor or diode). Other uses for the compositionsaccording to the present invention include coating materials for memorystorage devices, antistatic films, biosensors, electrochromic devices,solid electrolyte capacitors, energy storage devices such as arechargeable battery, and electromagnetic shielding applications.

One illustration of an organic electronic device structure is shown inFIG. 1. The device 100 has an anode layer 110 and a cathode layer 150,and a photoactive layer 130 between them. Adjacent to the anode is alayer 120 comprising a charge transport material, for example, a holetransport material. Adjacent to the cathode may be a charge transportlayer 140 comprising an electron transport material. As an option,devices may use one or more additional hole injection or hole transportlayers (not shown) next to the anode 110 and/or one or more additionalelectron injection or electron transport layers (not shown) next to thecathode 150.

As used herein, the term “photoactive” refers to a material that emitslight when activated by an applied voltage (such as in a light-emittingdiode or light-emitting electrochemical cell), or responds to radiantenergy and generates a signal with or without an applied bias voltage(such as in a photodetector). In one embodiment, a photoactive layer isan emitter layer.

Depending upon the application of the device 100, the photoactive layer130 can be a light-emitting layer that is activated by an appliedvoltage (such as in a light-emitting diode or light-emittingelectrochemical cell), a layer of material that responds to radiantenergy and generates a signal with or without an applied bias voltage(such as in a photodetector).

Examples of photodetectors include photoconductive cells,photoresistors, photoswitches, phototransistors, and photovoltaic cells,as these terms are described in Kirk-Othmer Concise Encyclopedia ofChemical Technology, 4^(th) edition, p. 1537, (1999).

In some embodiments, the hole transport layer 120 comprises at least onenew electroactive compound as described herein.

In some embodiments, the photoactive layer 130 comprises at least onenew electroactive compound as described herein, wherein theelectroactive compound is photoactive.

In some embodiments, the photoactive layer 130 comprises at least onenew electroactive compound as described herein, wherein theelectroactive compound serves as a host having a photoactive materialdispersed therein.

The other layers in the device can be made of any materials which areknown to be useful in such layers. The anode 110, is an electrode thatis particularly efficient for injecting positive charge carriers. It canbe made of, for example materials containing a metal, mixed metal,alloy, metal oxide or mixed-metal oxide, or it can be a conductingpolymer, and mixtures thereof. Suitable metals include the Group 11metals, the metals in Groups 4, 5, and 6, and the Group 8-10 transitionmetals. If the anode is to be light-transmitting, mixed-metal oxides ofGroups 12, 13 and 14 metals, such as indium-tin-oxide, are generallyused. The anode 110 may also comprise an organic material such aspolyaniline as described in “Flexible light-emitting diodes made fromsoluble conducting polymer,” Nature vol. 357, pp 477 479 (11 Jun. 1992).At least one of the anode and cathode should be at least partiallytransparent to allow the generated light to be observed.

In some embodiments, the device further comprises a buffer layer betweenthe anode and the layer comprising the new polymer. The term “bufferlayer” is intended to mean a layer comprising electrically conductive orsemiconductive materials and may have one or more functions in anorganic electronic device, including but not limited to, planarizationof the underlying layer, charge transport and/or charge injectionproperties, scavenging of impurities such as oxygen or metal ions, andother aspects to facilitate or to improve the performance of the organicelectronic device. Buffer materials may be polymers, oligomers, or smallmolecules, and may be in the form of solutions, dispersions,suspensions, emulsions, colloidal mixtures, or other compositions. Thebuffer layer can be formed with polymeric materials, such as polyaniline(PANI) or polyethylenedioxythiophene (PEDOT), which are often doped withprotonic acids. The protonic acids can be, for example,poly(styrenesulfonic acid), poly(2-acrylamido-2-methyl-1-propanesulfonicacid), and the like. The buffer layer can comprise charge transfercompounds, and the like, such as copper phthalocyanine and thetetrathiafulvalene-tetracyanoquinodimethane system (TTF-TCNQ). In oneembodiment, the buffer layer is made from a dispersion of a conductingpolymer and a colloid-forming polymeric acid. Such materials have beendescribed in, for example, published U.S. patent applications2004-0102577, 2004-0127637, and 2005/205860.

In some embodiments, hole transport layer 120 comprises the newelectroactive compound described herein. In some embodiments, holetransport layer 120 consists essentially of the new electroactivecompound described herein. In some embodiments, layer 120 comprisesother hole transport materials. Examples of other hole transportmaterials for layer 120 have been summarized for example, in Kirk OthmerEncyclopedia of Chemical Technology, Fourth Edition, Vol. 18, p. 837860, 1996, by Y. Wang. Both hole transporting molecules and polymers canbe used. Commonly used hole transporting molecules include, but are notlimited to:N,N′-diphenyl-N,N′-bis(3-methylphenyl)-[1,1′-biphenyl]-4,4′-diamine(TPD), 1,1-bis[(di-4-tolylamino) phenyl]cyclohexane (TAPC),N,N′-bis(4-methylphenyl)-N,N′-bis(4-ethylphenyl)-[1,1′-(3,3′-dimethyl)biphenyl]-4,4′-diamine(ETPD), tetrakis (3-methylphenyl)-N,N,N′,N′-2,5-phenylenediamine (PDA),a-phenyl 4-N,N-diphenylaminostyrene (TPS), p-(diethylamino)benzaldehydediphenylhydrazone (DEH), triphenylamine (TPA), bis[4(N,N-diethylamino)-2-methylphenyl](4-methylphenyl)methane (MPMP),1-phenyl-3-[p-(diethylamino)styryl]-5-[p-(diethylamino)phenyl]pyrazoline(PPR or DEASP), 1,2-trans-bis(9H-carbazol-9-yl)cyclobutane (DCZB),N,N,N′,N′ tetrakis(4-methylphenyl)-(1,1′-biphenyl)-4,4′-diamine (TTB),N,N′-Bis(naphthalen-1-yl)-N,N′-bis-(phenyl)benzidine (α-NPB), andporphyrinic compounds, such as copper phthalocyanine. Commonly used holetransporting polymers include, but are not limited to,polyvinylcarbazole, (phenylmethyl)polysilane, and polyaniline. It isalso possible to obtain hole transporting polymers by doping holetransporting molecules such as those mentioned above into polymers suchas polystyrene and polycarbonate. Buffer layers and/or hole transportlayer can also comprise polymers of thiophene, aniline, or pyrrole withpolymeric fluorinated sulfonic acids, as described in published USapplications 2004/102577, 2004/127637, and 2005/205860.

Any organic electroluminescent (“EL”) material can be used as thephotoactive material in layer 130. Such materials include, but are notlimited to, one of more compounds of the instant invention, smallorganic fluorescent compounds, fluorescent and phosphorescent metalcomplexes, conjugated polymers, and mixtures thereof. Examples offluorescent compounds include, but are not limited to, pyrene, perylene,rubrene, coumarin, derivatives thereof, and mixtures thereof. Examplesof metal complexes include, but are not limited to, metal chelatedoxinoid compounds, such as tris(8-hydroxyquinolato)aluminum (Alq3);cyclometalated iridium and platinum electroluminescent compounds, andmixtures thereof. Examples of conjugated polymers include, but are notlimited to poly(phenylenevinylenes), polyfluorenes,poly(spirobifluorenes), polythiophenes, poly(p-phenylenes), copolymersthereof, and mixtures thereof. The materials may also be present inadmixture with a host material. In some embodiments, the host materialis a hole transport material or an electron transport material. In someembodiments, the host is the new electroactive compound describedherein. In some embodiments, the ratio of host material to photoactivematerial is in the range of 5:1 to 20:1; in some embodiments, 10:1 to15:1. In some embodiments, the photoactive layer consists essentially ofa photoactive material and the new electroactive compound describedherein.

Examples of electron transport materials which can be used in theelectron transport layer 140 and/or the optional layer between layer 140and the cathode include metal chelated oxinoid compounds, such astris(8-hydroxyquinolato)aluminum (AIQ),bis(2-methyl-8-quinolinolato)(p-phenylphenolato) aluminum (BAIq),tetrakis-(8-hydroxyquinolato)hafnium (HfQ) andtetrakis-(8-hydroxyquinolato)zirconium (ZrQ); and azole compounds suchas 2-(4-biphenylyl)-5-(4-t-butylphenyl)-1,3,4-oxadiazole (PBD),3-(4-biphenylyl)-4-phenyl-5-(4-t-butylphenyl)-1,2,4-triazole (TAZ), and1,3,5-tri(phenyl-2-benzimidazole)benzene (TPBI); quinoxaline derivativessuch as 2,3-bis(4-fluorophenyl)quinoxaline; phenanthrolines such as4,7-diphenyl-1,10-phenanthroline (DPA) and2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (DDPA); and mixturesthereof.

The cathode 150, is an electrode that is particularly efficient forinjecting electrons or negative charge carriers. The cathode can be anymetal or nonmetal having a lower work function than the anode. Materialsfor the cathode can be selected from alkali metals of Group 1 (e.g., Li,Cs), the Group 2 (alkaline earth) metals, the Group 12 metals, includingthe rare earth elements and lanthanides, and the actinides. Materialssuch as aluminum, indium, calcium, barium, samarium and magnesium, aswell as combinations, can be used. Li-containing organometalliccompounds, LiF, and Li₂O can also be deposited between the organic layerand the cathode layer to lower the operating voltage.

The choice of materials for each of the component layers is preferablydetermined by balancing the goals of providing a device with high deviceefficiency with device operational lifetime. Other layers may also bepresent in the device. There may be one or more hole injection and/orhole transport layers between the buffer layer and the organic activelayer. There may be one or more electron transport layers and/orelectron injection layers between the organic active layer and thecathode.

The device can be prepared by a variety of techniques, includingsequentially depositing the individual layers on a suitable substrate.Substrates such as glass and polymeric films can be used. Conventionalvapor deposition techniques can be used, such as thermal evaporation,chemical vapor deposition, and the like. Alternatively, the organiclayers can be applied by liquid deposition using suitable solvents. Theliquid can be in the form of solutions, dispersions, or emulsions.Typical liquid deposition techniques include, but are not limited to,continuous deposition techniques such as spin coating, gravure coating,curtain coating, dip coating, slot-die coating, spray-coating, andcontinuous nozzle coating; and discontinuous deposition techniques suchas ink jet printing, gravure printing, and screen printing. anyconventional coating or printing technique, including but not limited tospin-coating, dip-coating, roll-to-roll techniques, ink jet printing,screen-printing, gravure printing and the like.

The new electroactive compounds described herein can be applied byliquid deposition from a liquid composition. The term “liquidcomposition” is intended to mean a liquid medium in which a material isdissolved to form a solution, a liquid medium in which a material isdispersed to form a dispersion, or a liquid medium in which a materialis suspended to form a suspension or an emulsion.

In one embodiment, the different layers have the following range ofthicknesses: anode 110, 500-5000 Å, in one embodiment 1000-2000 Å; holetransport layer 120, 50-2000 Å, in one embodiment 200-1000 Å;photoactive layer 130, 10-2000 Å, in one embodiment 100-1000 Å; layer140, 50-2000 Å, in one embodiment 100-1000 Å; cathode 150, 200-10000 Å,in one embodiment 300-5000 Å. The location of the electron-holerecombination zone in the device, and thus the emission spectrum of thedevice, can be affected by the relative thickness of each layer. Thusthe thickness of the electron-transport layer should be chosen so thatthe electron-hole recombination zone is in the light-emitting layer. Thedesired ratio of layer thicknesses will depend on the exact nature ofthe materials used.

In one embodiment, the device has the following structure, in order:anode, buffer layer, hole transport layer, photoactive layer, electrontransport layer, electron injection layer, cathode. In one embodiment,the anode is made of indium tin oxide or indium zinc oxide. In oneembodiment, the buffer layer comprises a conducting polymer selectedfrom the group consisting of polythiophenes, polyanilines, polypyrroles,copolymers thereof, and mixtures thereof. In one embodiment, the bufferlayer comprises a complex of a conducting polymer and a colloid-formingpolymeric acid.

In one embodiment, the hole transport layer comprises the new compounddescribed herein. In one embodiment, the hole transport layer comprisesa compound having triarylamine or triarylmethane groups. In oneembodiment, the hole transport layer comprises a material selected fromthe group consisting of TPD, MPMP, NPB, CBP, and mixtures thereof, asdefined above.

In one embodiment, the photoactive layer comprises an electroluminescentmetal complex and a host material. The host can be a charge transportmaterial. In one embodiment, the host is the new electroactive compounddescribed herein. In one embodiment, the electroluminescent complex ispresent in an amount of at least 1% by weight. In one embodiment, theelectroluminescent complex is 2-20% by weight. In one embodiment, theelectroluminescent complex is 20-50% by weight. In one embodiment, theelectroluminescent complex is 50-80% by weight. In one embodiment, theelectroluminescent complex is 80-99% by weight. In one embodiment, themetal complex is a cyclometalated complex of iridium, platinum, rhenium,or osmium. In one embodiment, the photoactive layer further comprises asecond host material.

In one embodiment, the electron transport layer comprises a metalcomplex of a hydroxyaryl-N-heterocycle. In one embodiment, thehydroxyaryl-N-heterocycle is unsubstituted or substituted8-hydroxyquinoline. In one embodiment, the metal is aluminum. In oneembodiment, the electron transport layer comprises a material selectedfrom the group consisting of tris(8-hydroxyquinolinato)aluminum,bis(8-hydroxyquinolinato)(4-phenylphenolato)aluminum,tetrakis(8-hydroxyquinolinato)zirconium,tetrakis(8-hydroxyquinolinato)hafnium, and mixtures thereof. In oneembodiment, the electron injection layer is LiF or Li₂O. In oneembodiment, the cathode is Al or Ba/Al. In one embodiment, there is anelectron transport layer comprising a material selected from the groupconsisting of tris(8-hydroxyquinolinato)aluminum,bis(8-hydroxyquinolinato)(4-phenylphenolato)aluminum,tetrakis(8-hydroxyquinolinato)zirconium,tetrakis(8-hydroxyquinolinato)hafnium, and mixtures thereof, and anelectron injection layer comprising LiF or Li₂O.

In one embodiment, the device is fabricated by liquid deposition of thebuffer layer, the hole transport layer, and the photoactive layer, andby vapor deposition of the electron transport layer, the electroninjection layer, and the cathode.

The buffer layer can be deposited from any liquid medium in which it isdissolved or dispersed and from which it will form a film. In oneembodiment, the liquid medium consists essentially of one or moreorganic solvents. In one embodiment, the liquid medium consistsessentially of water or water and an organic solvent. In one embodimentthe organic solvent is selected from the group consisting of alcohols,ketones, cyclic ethers, and polyols. In one embodiment, the organicliquid is selected from dimethylacetamide (“DMAc”), N-methylpyrrolidone(“NMP”), dimethylformamide (“DMF”), ethylene glycol (“EG”), aliphaticalcohols, and mixtures thereof. The buffer material can be present inthe liquid medium in an amount from 0.5 to 10 percent by weight. Otherweight percentages of buffer material may be used depending upon theliquid medium. The buffer layer can be applied by any continuous ordiscontinuous liquid deposition technique. In one embodiment, the bufferlayer is applied by spin coating. In one embodiment, the buffer layer isapplied by ink jet printing. After liquid deposition, the liquid mediumcan be removed in air, in an inert atmosphere, or by vacuum, at roomtemperature or with heating. In one embodiment, the layer is heated to atemperature less than 275° C. In one embodiment, the heating temperatureis between 100° C. and 275° C. In one embodiment, the heatingtemperature is between 100° C. and 120° C. In one embodiment, theheating temperature is between 120° C. and 140° C. In one embodiment,the heating temperature is between 140° C. and 160° C. In oneembodiment, the heating temperature is between 160° C. and 180° C. Inone embodiment, the heating temperature is between 180° C. and 200° C.In one embodiment, the heating temperature is between 200° C. and 220°C. In one embodiment, the heating temperature is between 190° C. and220° C. In one embodiment, the heating temperature is between 220° C.and 240° C. In one embodiment, the heating temperature is between 240°C. and 260° C. In one embodiment, the heating temperature is between260° C. and 275° C. The heating time is dependent upon the temperature,and is generally between 5 and 60 minutes. In one embodiment, the finallayer thickness is between 5 and 200 nm. In one embodiment, the finallayer thickness is between 5 and 40 nm. In one embodiment, the finallayer thickness is between 40 and 80 nm. In one embodiment, the finallayer thickness is between 80 and 120 nm. In one embodiment, the finallayer thickness is between 120 and 160 nm. In one embodiment, the finallayer thickness is between 160 and 200 nm.

The hole transport layer can be deposited from any liquid medium inwhich it is dissolved or dispersed and from which it will form a film.In one embodiment, the liquid medium consists essentially of one or moreorganic solvents. In one embodiment, the liquid medium consistsessentially of water or water and an organic solvent. In one embodimentthe organic solvent is an aromatic solvent. In one embodiment, theorganic liquid is selected from chloroform, dichloromethane, toluene,anisole, and mixtures thereof. The hole transport material can bepresent in the liquid medium in a concentration of 0.2 to 2 percent byweight. Other weight percentages of hole transport material may be useddepending upon the liquid medium. The hole transport layer can beapplied by any continuous or discontinuous liquid deposition technique.In one embodiment, the hole transport layer is applied by spin coating.In one embodiment, the hole transport layer is applied by ink jetprinting. After liquid deposition, the liquid medium can be removed inair, in an inert atmosphere, or by vacuum, at room temperature or withheating. In one embodiment, the layer is heated to a temperature of 300°C. or less. In one embodiment, the heating temperature is between 170°C. and 275° C. In one embodiment, the heating temperature is between170° C. and 200° C. In one embodiment, the heating temperature isbetween 190° C. and 220° C. In one embodiment, the heating temperatureis between 210° C. and 240° C. In one embodiment, the heatingtemperature is between 230° C. and 270° C. The heating time is dependentupon the temperature, and is generally between 5 and 60 minutes. In oneembodiment, the final layer thickness is between 5 and 50 nm. In oneembodiment, the final layer thickness is between 5 and 15 nm. In oneembodiment, the final layer thickness is between 15 and 25 nm. In oneembodiment, the final layer thickness is between 25 and 35 nm. In oneembodiment, the final layer thickness is between 35 and 50 nm.

The photoactive layer can be deposited from any liquid medium in whichit is dissolved or dispersed and from which it will form a film. In oneembodiment, the liquid medium consists essentially of one or moreorganic solvents. In one embodiment, the liquid medium consistsessentially of water or water and an organic solvent. In one embodimentthe organic solvent is an aromatic solvent. In one embodiment, theorganic liquid is selected from chloroform, dichloromethane, toluene,anisole, and mixtures thereof. The photoactive material can be presentin the liquid medium in a concentration of 0.2 to 2 percent by weight.Other weight percentages of photoactive material may be used dependingupon the liquid medium. The photoactive layer can be applied by anycontinuous or discontinuous liquid deposition technique. In oneembodiment, the photoactive layer is applied by spin coating. In oneembodiment, the photoactive layer is applied by ink jet printing. Afterliquid deposition, the liquid medium can be removed in air, in an inertatmosphere, or by vacuum, at room temperature or with heating. In oneembodiment, the deposited layer is heated to a temperature that is lessthan the Tg of the material having the lowest Tg. In one embodiment, theheating temperature is at least 10° C. less than the lowest Tg. In oneembodiment, the heating temperature is at least 20° C. less than thelowest Tg. In one embodiment, the heating temperature is at least 30° C.less than the lowest Tg. In one embodiment, the heating temperature isbetween 50° C. and 150° C. In one embodiment, the heating temperature isbetween 50° C. and 75° C. In one embodiment, the heating temperature isbetween 75° C. and 100° C. In one embodiment, the heating temperature isbetween 100° C. and 125° C. In one embodiment, the heating temperatureis between 125° C. and 150° C. The heating time is dependent upon thetemperature, and is generally between 5 and 60 minutes. In oneembodiment, the final layer thickness is between 25 and 100 nm. In oneembodiment, the final layer thickness is between 25 and 40 nm. In oneembodiment, the final layer thickness is between 40 and 65 nm. In oneembodiment, the final layer thickness is between 65 and 80 nm. In oneembodiment, the final layer thickness is between 80 and 100 nm.

The electron transport layer can be deposited by any vapor depositionmethod. In one embodiment, it is deposited by thermal evaporation undervacuum. In one embodiment, the final layer thickness is between 1 and100 nm. In one embodiment, the final layer thickness is between 1 and 15nm. In one embodiment, the final layer thickness is between 15 and 30nm. In one embodiment, the final layer thickness is between 30 and 45nm. In one embodiment, the final layer thickness is between 45 and 60nm. In one embodiment, the final layer thickness is between 60 and 75nm. In one embodiment, the final layer thickness is between 75 and 90nm. In one embodiment, the final layer thickness is between 90 and 100nm.

The electron injection layer can be deposited by any vapor depositionmethod. In one embodiment, it is deposited by thermal evaporation undervacuum. In one embodiment, the vacuum is less than 10⁻⁶ torr. In oneembodiment, the vacuum is less than 10⁻⁷ torr. In one embodiment, thevacuum is less than 10⁻⁸ torr. In one embodiment, the material is heatedto a temperature in the range of 100° C. to 400° C.; 150° C. to 350° C.preferably. All vapor deposition rates given herein are in units ofAngstroms per second. In one embodiment, the material is deposited at arate of 0.5 to 10 {acute over (Å)}/sec. In one embodiment, the materialis deposited at a rate of 0.5 to 1 {acute over (Å)}/sec. In oneembodiment, the material is deposited at a rate of 1 to 2 {acute over(Å)}/sec. In one embodiment, the material is deposited at a rate of 2 to3 {acute over (Å)}/sec. In one embodiment, the material is deposited ata rate of 3 to 4 {acute over (Å)}/sec. In one embodiment, the materialis deposited at a rate of 4 to 5 {acute over (Å)}/sec. In oneembodiment, the material is deposited at a rate of 5 to 6 {acute over(Å)}/sec. In one embodiment, the material is deposited at a rate of 6 to7 {acute over (Å)}/sec. In one embodiment, the material is deposited ata rate of 7 to 8 {acute over (Å)}/sec. In one embodiment, the materialis deposited at a rate of 8 to 9 {acute over (Å)}/sec. In oneembodiment, the material is deposited at a rate of 9 to 10 {acute over(Å)}/sec. In one embodiment, the final layer thickness is between 0.1and 3 nm. In one embodiment, the final layer thickness is between 0.1and 1 nm. In one embodiment, the final layer thickness is between 1 and2 nm. In one embodiment, the final layer thickness is between 2 and 3nm.

The cathode can be deposited by any vapor deposition method. In oneembodiment, it is deposited by thermal evaporation under vacuum. In oneembodiment, the vacuum is less than 10⁻⁶ torr. In one embodiment, thevacuum is less than 10⁻⁷ torr. In one embodiment, the vacuum is lessthan 10⁻⁸ torr. In one embodiment, the material is heated to atemperature in the range of 100° C. to 400° C.; 150° C. to 350° C.preferably. In one embodiment, the material is deposited at a rate of0.5 to 10 {acute over (Å)}/sec. In one embodiment, the material isdeposited at a rate of 0.5 to 1 {acute over (Å)}/sec. In one embodiment,the material is deposited at a rate of 1 to 2 {acute over (Å)}/sec. Inone embodiment, the material is deposited at a rate of 2 to 3 {acuteover (Å)}/sec. In one embodiment, the material is deposited at a rate of3 to 4 {acute over (Å)}/sec. In one embodiment, the material isdeposited at a rate of 4 to 5 {acute over (Å)}/sec. In one embodiment,the material is deposited at a rate of 5 to 6 {acute over (Å)}/sec. Inone embodiment, the material is deposited at a rate of 6 to 7 {acuteover (Å)}/sec. In one embodiment, the material is deposited at a rate of7 to 8 {acute over (Å)}/sec. In one embodiment, the material isdeposited at a rate of 8 to 9 {acute over (Å)}/sec. In one embodiment,the material is deposited at a rate of 9 to 10 {acute over (Å)}/sec. Inone embodiment, the final layer thickness is between 10 and 10000 nm. Inone embodiment, the final layer thickness is between 10 and 1000 nm. Inone embodiment, the final layer thickness is between 10 and 50 nm. Inone embodiment, the final layer thickness is between 50 and 100 nm. Inone embodiment, the final layer thickness is between 100 and 200 nm. Inone embodiment, the final layer thickness is between 200 and 300 nm. Inone embodiment, the final layer thickness is between 300 and 400 nm. Inone embodiment, the final layer thickness is between 400 and 500 nm. Inone embodiment, the final layer thickness is between 500 and 600 nm. Inone embodiment, the final layer thickness is between 600 and 700 nm. Inone embodiment, the final layer thickness is between 700 and 800 nm. Inone embodiment, the final layer thickness is between 800 and 900 nm. Inone embodiment, the final layer thickness is between 900 and 1000 nm. Inone embodiment, the final layer thickness is between 1000 and 2000 nm.In one embodiment, the final layer thickness is between 2000 and 3000nm. In one embodiment, the final layer thickness is between 3000 and4000 nm. In one embodiment, the final layer thickness is between 4000and 5000 nm. In one embodiment, the final layer thickness is between5000 and 6000 nm. In one embodiment, the final layer thickness isbetween 6000 and 7000 nm. In one embodiment, the final layer thicknessis between 7000 and 8000 nm. In one embodiment, the final layerthickness is between 8000 and 9000 nm. In one embodiment, the finallayer thickness is between 9000 and 10000 nm.

In one embodiment, the device is fabricated by vapor deposition of thebuffer layer, the hole transport layer, and the photoactive layer, theelectron transport layer, the electron injection layer, and the cathode.

In one embodiment, the buffer layer is applied by vapor deposition. Inone embodiment, it is deposited by thermal evaporation under vacuum. Inone embodiment, the vacuum is less than 10⁻⁶ torr. In one embodiment,the vacuum is less than 10⁻⁷ torr. In one embodiment, the vacuum is lessthan 10⁻⁸ torr. In one embodiment, the material is heated to atemperature in the range of 100° C. to 400° C.; 150° C. to 350° C.preferably. In one embodiment, the material is deposited at a rate of0.5 to 10 {acute over (Å)}/sec. In one embodiment, the material isdeposited at a rate of 0.5 to 1 {acute over (Å)}/sec. In one embodiment,the material is deposited at a rate of 1 to 2 {acute over (Å)}/sec. Inone embodiment, the material is deposited at a rate of 2 to 3 {acuteover (Å)}/sec. In one embodiment, the material is deposited at a rate of3 to 4 {acute over (Å)}/sec. In one embodiment, the material isdeposited at a rate of 4 to 5 {acute over (Å)}/sec. In one embodiment,the material is deposited at a rate of 5 to 6 {acute over (Å)}/sec. Inone embodiment, the material is deposited at a rate of 6 to 7 {acuteover (Å)}/sec. In one embodiment, the material is deposited at a rate of7 to 8 {acute over (Å)}/sec. In one embodiment, the material isdeposited at a rate of 8 to 9 {acute over (Å)}/sec. In one embodiment,the material is deposited at a rate of 9 to 10 {acute over (Å)}/sec. Inone embodiment, the final layer thickness is between 5 and 200 nm. Inone embodiment, the final layer thickness is between 5 and 30 nm. In oneembodiment, the final layer thickness is between 30 and 60 nm. In oneembodiment, the final layer thickness is between 60 and 90 nm. In oneembodiment, the final layer thickness is between 90 and 120 nm. In oneembodiment, the final layer thickness is between 120 and 150 nm. In oneembodiment, the final layer thickness is between 150 and 280 nm. In oneembodiment, the final layer thickness is between 180 and 200 nm.

In one embodiment, the hole transport layer is applied by vapordeposition. In one embodiment, it is deposited by thermal evaporationunder vacuum. In one embodiment, the vacuum is less than 10⁻⁶ torr. Inone embodiment, the vacuum is less than 10⁻⁷ torr. In one embodiment,the vacuum is less than 10⁻⁸ torr. In one embodiment, the material isheated to a temperature in the range of 100° C. to 400° C.; 150° C. to350° C. preferably. In one embodiment, the material is deposited at arate of 0.5 to 10 {acute over (Å)}/sec. In one embodiment, the materialis deposited at a rate of 0.5 to 1 {acute over (Å)}/sec. In oneembodiment, the material is deposited at a rate of 1 to 2 {acute over(Å)}/sec. In one embodiment, the material is deposited at a rate of 2 to3 {acute over (Å)}/sec. In one embodiment, the material is deposited ata rate of 3 to 4 {acute over (Å)}/sec. In one embodiment, the materialis deposited at a rate of 4 to 5 {acute over (Å)}/sec. In oneembodiment, the material is deposited at a rate of 5 to 6 {acute over(Å)}/sec. In one embodiment, the material is deposited at a rate of 6 to7 {acute over (Å)}/sec. In one embodiment, the material is deposited ata rate of 7 to 8 {acute over (Å)}/sec. In one embodiment, the materialis deposited at a rate of 8 to 9 {acute over (Å)}/sec. In oneembodiment, the material is deposited at a rate of 9 to 10 {acute over(Å)}/sec. In one embodiment, the final layer thickness is between 5 and200 nm. In one embodiment, the final layer thickness is between 5 and 30nm. In one embodiment, the final layer thickness is between 30 and 60nm. In one embodiment, the final layer thickness is between 60 and 90nm. In one embodiment, the final layer thickness is between 90 and 120nm. In one embodiment, the final layer thickness is between 120 and 150nm. In one embodiment, the final layer thickness is between 150 and 280nm. In one embodiment, the final layer thickness is between 180 and 200nm.

In one embodiment, the photoactive layer is applied by vapor deposition.In one embodiment, it is deposited by thermal evaporation under vacuum.In one embodiment, the photoactive layer consists essentially of asingle electroluminescent compound, which is deposited by thermalevaporation under vacuum. In one embodiment, the vacuum is less than10⁻⁶ torr. In one embodiment, the vacuum is less than 10⁻⁷ torr. In oneembodiment, the vacuum is less than 10⁻⁸ torr. In one embodiment, thematerial is heated to a temperature in the range of 100° C. to 400° C.;150° C. to 350° C. preferably. In one embodiment, the material isdeposited at a rate of 0.5 to 10 {acute over (Å)}/sec. In oneembodiment, the material is deposited at a rate of 0.5 to 1 {acute over(Å)}/sec. In one embodiment, the material is deposited at a rate of 1 to2 {acute over (Å)}/sec. In one embodiment, the material is deposited ata rate of 2 to 3 {acute over (Å)}/sec. In one embodiment, the materialis deposited at a rate of 3 to 4 {acute over (Å)}/sec. In oneembodiment, the material is deposited at a rate of 4 to 5 {acute over(Å)}/sec. In one embodiment, the material is deposited at a rate of 5 to6 {acute over (Å)}/sec. In one embodiment, the material is deposited ata rate of 6 to 7 {acute over (Å)}/sec. In one embodiment, the materialis deposited at a rate of 7 to 8 {acute over (Å)}/sec. In oneembodiment, the material is deposited at a rate of 8 to 9 {acute over(Å)}/sec. In one embodiment, the material is deposited at a rate of 9 to10 {acute over (Å)}/sec. In one embodiment, the final layer thickness isbetween 5 and 200 nm. In one embodiment, the final layer thickness isbetween 5 and 30 nm. In one embodiment, the final layer thickness isbetween 30 and 60 nm. In one embodiment, the final layer thickness isbetween 60 and 90 nm. In one embodiment, the final layer thickness isbetween 90 and 120 nm. In one embodiment, the final layer thickness isbetween 120 and 150 nm. In one embodiment, the final layer thickness isbetween 150 and 280 nm. In one embodiment, the final layer thickness isbetween 180 and 200 nm.

In one embodiment, the photoactive layer comprises twoelectroluminescent materials, each of which is applied by thermalevaporation under vacuum. Any of the above listed vacuum conditions andtemperatures can be used. Any of the above listed deposition rates canbe used. The relative deposition rates can be from 50:1 to 1:50. In oneembodiment, the relative deposition rates are from 1:1 to 1:3. In oneembodiment, the relative deposition rates are from 1:3 to 1:5. In oneembodiment, the relative deposition rates are from 1:5 to 1:8. In oneembodiment, the relative deposition rates are from 1:8 to 1:10. In oneembodiment, the relative deposition rates are from 1:10 to 1:20. In oneembodiment, the relative deposition rates are from 1:20 to 1:30. In oneembodiment, the relative deposition rates are from 1:30 to 1:50. Thetotal thickness of the layer can be the same as that described above fora single-component photoactive layer.

In one embodiment, the photoactive layer comprises oneelectroluminescent material and at least one host material, each ofwhich is applied by thermal evaporation under vacuum. Any of the abovelisted vacuum conditions and temperatures can be used. Any of the abovelisted deposition rates can be used. The relative deposition rate ofelectroluminescent material to host can be from 1:1 to 1:99. In oneembodiment, the relative deposition rates are from 1:1 to 1:3. In oneembodiment, the relative deposition rates are from 1:3 to 1:5. In oneembodiment, the relative deposition rates are from 1:5 to 1:8. In oneembodiment, the relative deposition rates are from 1:8 to 1:10. In oneembodiment, the relative deposition rates are from 1:10 to 1:20. In oneembodiment, the relative deposition rates are from 1:20 to 1:30. In oneembodiment, the relative deposition rates are from 1:30 to 1:40. In oneembodiment, the relative deposition rates are from 1:40 to 1:50. In oneembodiment, the relative deposition rates are from 1:50 to 1:60. In oneembodiment, the relative deposition rates are from 1:60 to 1:70. In oneembodiment, the relative deposition rates are from 1:70 to 1:80. In oneembodiment, the relative deposition rates are from 1:80 to 1:90. In oneembodiment, the relative deposition rates are from 1:90 to 1:99. Thetotal thickness of the layer can be the same as that described above fora single-component photoactive layer.

In one embodiment, the electron transport layer is applied by vapordeposition. In one embodiment, it is deposited by thermal evaporationunder vacuum. In one embodiment, the vacuum is less than 10⁻⁶ torr. Inone embodiment, the vacuum is less than 10⁻⁷ torr. In one embodiment,the vacuum is less than 10⁻⁸ torr. In one embodiment, the material isheated to a temperature in the range of 100° C. to 400° C.; 150° C. to350° C. preferably. In one embodiment, the material is deposited at arate of 0.5 to 10 {acute over (Å)}/sec. In one embodiment, the materialis deposited at a rate of 0.5 to 1 {acute over (Å)}/sec. In oneembodiment, the material is deposited at a rate of 1 to 2 {acute over(Å)}/sec. In one embodiment, the material is deposited at a rate of 2 to3 {acute over (Å)}/sec. In one embodiment, the material is deposited ata rate of 3 to 4 {acute over (Å)}/sec. In one embodiment, the materialis deposited at a rate of 4 to 5 {acute over (Å)}/sec. In oneembodiment, the material is deposited at a rate of 5 to 6 {acute over(Å)}/sec. In one embodiment, the material is deposited at a rate of 6 to7 {acute over (Å)}/sec. In one embodiment, the material is deposited ata rate of 7 to 8 {acute over (Å)}/sec. In one embodiment, the materialis deposited at a rate of 8 to 9 {acute over (Å)}/sec. In oneembodiment, the material is deposited at a rate of 9 to 10 {acute over(Å)}/sec. In one embodiment, the final layer thickness is between 5 and200 nm. In one embodiment, the final layer thickness is between 5 and 30nm.

In one embodiment, the final layer thickness is between 30 and 60 nm. Inone embodiment, the final layer thickness is between 60 and 90 nm. Inone embodiment, the final layer thickness is between 90 and 120 nm. Inone embodiment, the final layer thickness is between 120 and 150 nm. Inone embodiment, the final layer thickness is between 150 and 280 nm. Inone embodiment, the final layer thickness is between 180 and 200 nm.

In one embodiment, the electron injection layer is applied by vapordeposition, as described above.

In one embodiment, the cathode is applied by vapor deposition, asdescribe above.

In one embodiment, the device is fabricated by vapor deposition of someof the organic layers, and liquid deposition of some of the organiclayers. In one embodiment, the device is fabricated by liquid depositionof the buffer layer, and vapor deposition of all of the other layersAlthough methods and materials similar or equivalent to those describedherein can be used in the practice or testing of the present invention,suitable methods and materials are described below. In addition, thematerials, methods, and examples are illustrative only and not intendedto be limiting. All publications, patent applications, patents, andother references mentioned herein are incorporated by reference in theirentirety.

EXAMPLES

The concepts described herein will be further described in the followingexamples, which do not limit the scope of the invention described in theclaims.

Example 1

This example illustrates the preparation of an electroactive compound,Compound C.

Part 1—Intermediate Compound 2:

Compound 1 (4.0 g, 6.3 mmol) was dissolved in 60 mL toluene in a 2 neck200 mL septum-sealed round bottom.4-[(tert-Butoxycarbonyl)amino]benzeneboronic acid (3.72 g, 15.7 mmol),Aliquat® 336 (0.5 g) and sodium carbonate (3.33 g, 31.4 mmol) wereadded. The mixture was sparged with nitrogen and the reaction flask wasfitted with a reflux condenser and nitrogen inlet-outlet. In a nitrogenpurged glovebox, tetrakistriphenylphosphine (363 mg, 5.00 mol %) andanhydrous toluene (10 mL) were combined in a round bottom flask. Theflask was sealed with a septum and removed from the glovebox. Thecatalyst suspension was added to the reaction mixture via a cannula.Water (30 mL) was added to the reaction vessel via syringe. The nitrogensparge was removed and replaced with a nitrogen blanket. The reactionmixture was heated at 90° C. for 3 h. The reaction was allowed to coolto room temperature, transferred to a separatory funnel and diluted withethyl acetate. The aqueous layer was removed and the organic layer waswashed with water, then with brine and dried over MgSO₄. The crudeproduct was filtered through a pad of silica gel, rinsing with ethylacetate. The solvent was removed and the product was dried under highvacuum. After purification by flash column chromatography (3:2hexanes:methylene chloride), 2.2 g of a light orange foamy solid wasobtained. Purity (HPLC): 98.5%, pure 4,4′ isomer. NMR analysis confirmedthe structure of Intermediate Compound 2.

Part 2—Intermediate Compound 3:

Intermediate Compound 2 (2.2 g, 2.5 mmol) was dissolved in 40 mLmethylene chloride in a 250 mL round bottom flask equipped with amagnetic stirrer and a nitrogen inlet-outlet. Trifluoroacetic acid (2.9g, 25 mmol) was added and the reaction was allowed to stir for 16 h. Thesolvent and trifluoroacetic acid were removed by rotary evaporation andthe product was taken up in diethyl ether. The diethyl ether solutionwas washed with saturated sodium bicarbonate (2×), water and brine. Theether layer was dried over MgSO4, filtered and concentrated on a rotaryevaporator. The product was dried under high vacuum to yield 1.7 g(100%) of a light orange foamy solid. Purity (HPLC): 94.7%. NMR analysisconfirmed the structure of Intermediate Compound 3.

Part 3—Intermediate Compound 4:

In a nitrogen purged glovebox, combined 3 (1.60 g, 2.42 mmol),4-bromobiphenyl (1.13 g, 4.84 mmol),tris(dibenzylideneacetone)dipalladium(0) (55 mg, 2.5 mol %),tri-t-butylphosphine (25 mg, 5 mol %) and toluene (30 mL) in a 500 mLround bottom flask equipped with a magnetic stirrer. Sodium t-butoxide(0.58 g, 6.05 mmol) was added and the reaction flask was capped. After72 h, the reaction mixture was removed from the glovebox and filteredthrough a pad of solica gel, rinsing with toluene. The solution wasconcentrated on a rotary evaporator and dried under high vacuum. Theproduct was purified by flash chromatography on silica gel (7:3 to 3:2hexanes:methylene chloride gradient) to give 1.56 g of a white solid.NMR analysis confirmed the structure of Intermediate Compound 4.

Part 5—Intermediate Compound 5.

In a nitrogen purged glovebox, combined 4 (1.50 g, 1.55 mmol),p-bromoiodobenzene (1.32 g, 4.66 mmol),tris(dibenzylideneacetone)dipalladium(0) (36 mg, 2.5 mol %),bis(diphenylphosphinoferrocene) (43 mg, 5 mol %) and toluene (60 mL) ina 300 mL round bottom flask equipped with a magnetic stirrer. Sodiumt-butoxide (0.373 g, 3.88 mmol) was added and the reaction vessel wascapped and removed from the glovebox. A condenser and nitrogeninlet-outlet was fitted to the round bottom flask and the reaction washeated to 85° C. with an oil bath. After 20 h, a suspension ofp-bromoiodobenzene (0.66 g, 2.3 mmol),tris(dibenzylideneacetone)dipalladium(0) (18 mg, 1.25 mol %),bis(diphenylphosphino)ferrocene (21 mg, 2.5 mol %) and sodium t-butoxide(186 mg, 1.25 mol %) in toluene (10 mL) was prepared in the glovebox andtransferred to the reaction mixture via cannula. After additional 20 hat 90° C., the reaction mixture was cooled to room temperature. Thereaction mixture was filtered through a pad of silica gel rinsing withtoluene and then concentrated on a rotary evaporator. The crude productwas dried under high vacuum. The product was purified by flashchromatography on silica gel (6:1-5:1 hexanes:methylene chloridegradient) to give 1.4 g of a white solid. Purity (UPLC): >99.9%. NMRanalysis confirmed the structure of Intermediate Compound 5.

Part 6—Compound C:

All operations were carried out in a nitrogen purged glovebox unlessotherwise noted. Monomer 5 (1.35 g, 1.06 mmol) was added to ascintillation vial and dissolved in 13 mL toluene. A clean, dry 50 mLSchlenk tube was charged with bis(1,5-cyclooctadiene)nickel(0) (0.597 g,2.17 mmol). 2,2′-Dipyridyl (0.339 g, 2.17 mmol) and 1,5-cyclooctadiene(0.235 g, 2.02 mmol) were weighed into a scintillation vial anddissolved in 2 mL N,N′-dimethylformamide. The solution was added to theSchlenk tube. The Schlenk tube was inserted into an aluminum block andthe block was heated and stirred on a hotplate/stirrer at a setpointthat resulted in an internal temperature of 60° C. The catalyst systemwas held at 60° C. for 30 minutes and then raised to 70° C. The monomersolution in toluene was added to the Schlenk tube and the tube wassealed. The polymerization mixture was stirred at 70° C. for 18 h. After18 h, the Schlenk tube was removed from the block and allowed to cool toroom temperature. The tube was removed from the glovebox and thecontents were poured into a solution of conc. HCl/MeOH (1.5% v/v conc.HCl). After stirring for 2 h, the polymer was collected by vacuumfiltration and dried under high vacuum. The polymer was purified bysuccessive precipitations from toluene into HCl/MeOH (1% v/v conc. HCl),MeOH, toluene (CMOS grade), and 3-pentanone. A white, fibrous polymer(1.1 g) was obtained. The molecular weight of the polymer was determinedby GPC (THF mobile phase, polystyrene standards): M_(w)=427,866;M_(n)=103,577; M_(w)/M_(n)=4.13. NMR analysis confirmed the structure ofCompound C.

Example 2 Synthesis of Compound S

Part 1—Synthesis of Intermediate Compound 7:

Part 2: Synthesis of intermediate Compound 8

1,4-dibromo-2,5-dihexyl benzene (8.05 mmoles, 3.255 g), boronic ester 7(17.7 mmoles, 7.545 g), Na₂CO₃ (40.3 mmoles, 4.268 g) and Aliquat 336(0.500 g) were suspended in toluene (100 mL) in a 250 mLtwo-necked-round-bottom-flask with stir bar and condenser. Reactionmixture degassed for 30 minutes. Pd(PPh₃)₄ (0.403 mmoles, 0.465 g) addedas a powder to reaction mixture. Reaction mixture degassed for a further15 minutes, whilst simultaneously degassing water (50 mL). Water addedvia syringe to reaction vessel. Reaction heated to 90° C. for two days.Resulting reaction mixture diluted with ethyl acetate (150 mL), washedwith ethyl acetate (3×100 mL). Organic layer washed with brine (2×100mL), dried over magnesium sulfate, filtered and concentrated.Purification by column chromatography on silica gel using 1:3dichloromethane:Hexanes to yield white powder (56%, 3.8 g). ¹H NMR (500MHz, CD₂Cl₂) δ=7.45 (d, J=8.5 Hz, 4H), 7.33-7.31 (m, 5H), 7.26-7.19 (m,5H), 6.65 (s, 2H), 2.71-2.63 (m, 9H), 1.54 (s, 18H), 1.31-1.20 (m, 14H),1.15 (t, J=7.49, 7H), 0.83 (t, J=6.85 Hz, 6H).

Part 3: Synthesis of Intermediate Compound 9

Compound 8 (4.54 mmoles, 3.800 g) was added to 200 mL round bottom flaskand dissolved in dichloromethane (90 mL). Trifluoroacetic acid (45.4mmoles, 5.175 g) added dropwise to the solution. After one daydichloromethane removed by rotary evaporation and the resulting greypowder dissolved in ethyl ether (100 mL) to which sodium bicarbonate wasadded (100 mL). The organic layer was washed with water (2×100 mL),followed by brine (2×100 mL). After it was dried over magnesium sulfateand concentrated to yield an off white powder (100%, 2.891 g). ¹H NMR(500 MHz, CD₂Cl₂) δ=7.28 (m, 2H), 7.23-7.18 (m, 6H), 7.16 (d, J=8.47 Hz,4H), 6.76 (d, J=8.37 Hz, 4H), 3.77 (s, 4H), 2.71-2.63 (m, 6H), 1.3-1.19(m, 16H), 1.15 (t, J=7.5 Hz, 8H), 0.83 (t, J=6.86 Hz, 6H).

Part 4: Synthesis of Intermediate Compound 10

In a 250 mL flask equipped with stirrer bar compound 9 (4.539 mmoles,2.891 g), bromobiphenyl (9.123 mmoles, 2.127 g) and toluene (65 mL) wereadded, followed by Pd₂(dba)₃ (0.227 mmole, 0.208 g), P^(t)Bu₃ (0.454mmole, 0.092 g) and NaO^(t)Bu (9.078 mmoles, 0.845 g). Three days laterthe resulting reaction mixture was diluted with toluene (100 mL),filtered through a pad of silica and celite washed with toluene (3×100mL), followed by ethyl acetate (2×100 mL) and concentrated to a brownsolid. Purification was performed by column chromatography on silica gelusing eluent 1:6 Ethyl acetate:Hexanes, to yield a white powder (55%,2.367 g). ¹H NMR (500 MHz, CD₂Cl₂) δ=7.61 (d, J=7.24 Hz, 4H), 7.57 (d,J=8.51 Hz, 4H), 7.43 (t, J=7.6 Hz, 4H), 7.34-7.28 (m, 12H), 5.99 (s,2H), 2.73 (q, J=Hz, 4H), 2.66 (t, J=7.7 Hz, 6H), 1.33-1.17 (m, 20H),0.84 (t, J=7.2 Hz, 6H).

Part 5: Synthesis of Intermediate Compound 11

Compound 10 (2.515 mmoles, 2.367 g), 1-bromo-4-iodo benzene (3.772mmoles, 1.067 g), Pd₂(dba)₃ (0.126 mmoles, 0.115 g), 1,1-Bis(diphenylphosphino) ferrocene (0.251 mmoles, 0.139 g) and sodiumt-butoxide (2.766 mmoles, 0.266 g) were suspended in toluene (100 mL) ina 200 mL two-necked-round-bottom-flask fitted with condenser and stirbar. Reaction mixture heated at 90° C. for two days. The reactionmixture was filtered through a pad of silica and celite, washed withtoluene (2×200 mL) and concentrated to form brown solid. Purification bycolumn chromatography on silica gel using 1:2 dichloromethane:hexanes,The product was washed with MeOH to give white powder (23%, 0.715 g). ¹HNMR (500 MHz, CD₂Cl₂) δ=7.61 (d, J=6.95 Hz, 4H), 7.56 (d, J=8.73 Hz,4H), 7.46-7.4 (m, 8H), 7.34-7.29 (m, 10H), 7.24-7.18 (m, 12H), 7.08 (d,J=8.89 Hz, 4H), 2.74 (q, J=7.5 Hz, 4H), 2.65 (t J=8.12 Hz, 6H),1.32-1.18 (m, 22H), 0.83 (t, J=6.88 Hz, 6H).

Part 6—Polymerization of Compound 11.

The polymerization of compound 11 performed as described for compound C.The polymer was obtained as a white solid. The molecular weight of thepolymer was determined by GPC (THF mobile phase, polystyrene standards):M_(w)=140,399; M_(n)=47,692; M_(w)/M_(n)=2.04. NMR analysis confirmedthe structure of Compound S.

Example 3 Synthesis of Compound T

Part 1. Synthesis of Intermediate 1-Bromo-4′-(nitrophenyl)naphthalene(12)

To a 300 ml 2-neck round bottom flask equipped with reflux condenser andnitrogen bubbler were added 1,4-dibromonaphthalene (15.5 g, 54.2 mmol)and 4-nitrophenyl boronic acid (9.05 g, 54.2 mmol). Toluene (175 ml) wasadded, then 2.0 M aq Na₂CO₃ (56.9 ml, 113.8 mmol), then Aliquat336®(2.19 g, 5.42 mmol). The mixture was sparged with nitrogen for 1 hour.The reaction was heated under nitrogen for 20 hours and then cooled toroom temperature. The mixture was diluted with toluene, washed threetimes with water and once with brine. The organic layer was dried overMgSO₄, filtered, concentrated on a rotary evaporator and dried underhigh vacuum to give 22 g of brown solid. The crude product was purifiedby column chromatography (silica gel, 4:1 Hex:CH₂Cl₂) to isolate 7.9 gwhite solid. Yield: 40%. ¹H NMR analysis (500 MHz, CD₂Cl₂) wasconsistent with structure 12.

Part 2. Synthesis of Intermediate 1-(Aminophenyl)-4′-bromonaphthalene(13)

To a 500 ml round-bottom flask equipped with stir bar, reflux condenser,and nitrogen bubbler were added compound 1 (7 g, 20 mmol), THF (170 ml),tin chloride dihydrate (19.25 g, 85.32 mmol), and aqueous 1M HCl (64 ml,64 mmol). The reaction was heated at reflux under nitrogen for 1 hour,then cooled to room temperature. The mixture was concentrated on arotary evaporator to remove THF and neutralized with a saturatedsolution of aq. NaHCO₃. The aqueous layer was extracted with diethylether (3×). The organic layer was washed with brine, dried over MgSO₄,filtered, concentrated on a rotary evaporator and dried under highvacuum to give 4.5 g crude product. The crude product was purified bycolumn chromatography (silica gel, CH₂Cl₂) to give 4.36 g light-orangesolid. Yield: 69%. Purity (GC-MS): 99+%. ¹H NMR (500 MHz, CD₂Cl₂) isconsistent with product structure.

Part 3. Synthesis of intermediate 1-Bromo-4′-(iodophenyl)naphthalene(14)

To a 200 ml round-bottom flask equipped with a stir bar and nitrogenbubbler were added compound 2 (3.85 g, 12.9 mmol), THF (65 ml), andaqueous conc. HCl (13 ml). The reaction mixture was cooled in anice/water bath to 0° C. NaNO₂ (1.07 g, 15.5 mmol) in 13 ml H₂O was addeddropwise and the mixture was stirred with cooling for 25 minutes. KI(4.29 g, 25.8 mmol) in 13 ml H₂O was added dropwise. The reactionmixture was warmed slowly to room temperature and stirred for 16 hours.The reaction was diluted with water and extracted with diethyl ether.The organic layer was washed with water, saturated aq. NaHCO₃, saturatedaq. NaHSO₃ and brine. The organic layer was dried over MgSO₄, filtered,concentrated on a rotary evaporator and dried under high vacuum to give4.68 g crude product. The crude product was recrystallized from 1:1MeOH:ethyl acetate to give 2.53 g light orange solid. Yield: 48%. Purity(GC-MS): 99+%. ¹H NMR (500 MHz, CD₂Cl₂) is consistent with productstructure.

Part 4. Synthesis of Intermediate Compound 15

Diamine 4 (mixture of 4,4′- and 4,5′-isomers) (1.75 g, 1.81 mmol), 14(1.85 g, 4.52 mmol), bis(diphenylphosphinoferrocene) (50 mg, 0.91 mmol),tris(dibenzylideneacetone)dipalladium(0) (40 mg, 0.05 mmol), toluene (50ml) and then sodium t-butoxide (0.44 g, 4.5 mmol) were weighed into a250 mL round bottom flask in a nitrogen purged glovebox. The reactionvessel was capped, removed from the gloved box and equipped with areflux condenser and nitrogen bubbler. The reaction was heated at 90° C.for 18 hours. The reaction mixture was filtered through a plug of silicagel, rinsing with dichloromethane. The filtrate was concentrated on arotary evaporator and dried under high vacuum to give 3.5 gbrownish-orange oil. The crude product was purified by columnchromatography (3:1 hexanes:CH₂Cl₂ gradient to 3:2 hexanes:CH₂Cl₂) toisolate 2.15 g product which was a mixture of 4,4′- and 4,5′-isomers.Yield: 78.2%. ¹H NMR (500 MHz, CD₂Cl₂) is consistent with structure of15.

Part 5. Synthesis of Compound T

The polymerization of 5 was carried out in a nitrogen purged glovebox.Bis(1,5-cyclooctadiene)nickel(0) (0.277 g, 1.01 mmol) was added to a 25ml Schlenk tube. 2,2′-Dipyridyl (0.157 g, 1.01 mmol) and1,5-cyclooctadiene (0.109 g, 1.01 mmol) were dissolved in 2 mL DMF. Thissolution was added to the nickel catalyst. The catalyst solution wasstirred and heated in an aluminum block at 60° C. for 30 minutes. Thetemperature of the heating block was raised to 70° C. Compound 15 (0.750g, 0.491 mmol) dissolved in toluene (13 mL) and then added to thecatalyst solution. The Schlenk tube was sealed and heated for 22 hoursand then cooled to room temperature. The reaction tube was removed fromthe dry box and the contents were poured into 1.5 v/v % HCl/MeOH. Thepolymer was purified by two precipitations into 1.5 v/v % HCl/MeOH andone precipitation from toluene into MeOH. The polymer was isolated byfiltration and then dissolved in toluene. The toluene solution waspassed through a plug of silica gel. The filtrate was concentrated andpoured into 3-pentanone. The polymer was collected by vacuum filtration,re-dissolved in toluene and passed through a plug of Florisil®. Thefiltrate was concentrated and precipitated from 3-pentanone. The polymerwas isolated by filtration and dried under high vacuum to give 0.52 gwhite, fibrous polymer. Yield: 77%. Molecular weight determination (GPC,THF, polystyrene standards): M_(w)=296,000; M_(n)=103,000; PDI=2.88.

Example 4 Synthesis of Compound U

The monomer 16 was synthesized following the procedure outlined forcompound 5 except that 4-vinyl-4′-bromobiphenyl was used instead ofbromobiphenyl.

Compounds 5 (0.95 mmol) and 16 (0.05 mmol) were copolymerized followingthe procedure for the synthesis of compound C to obtain a white fibrouspolymer in 86% yield (0.96 g). Molecular weight determination (GPC, THF,polystyrene standards): M_(w)=658,109; M_(n)=105,822; PDI=6.22.

Example 5 Synthesis of Compound V

Compound V was synthesized using the route shown below:

Part 1. Synthesis of Intermediate 18:

In a nitrogen purged glove box, ditriflate 17 (3.2 g, 4.38 mmol) and2-ethyl-4′-octyl-biphen-4-yl-amine (2.84 g, 9.19 mmol) were dissolved intoluene (60 mL) in a 200 mL of round bottom flask, followed by theaddition of the toluene (10 mL) solution oftris(dibenzylideneacetone)dipalladium(0) (108 mg, 0.027 eq.) and1,1′-bis(diphenylphosphino)ferrocene (128 mg, 0.053 eq) to the mixture.After stirring the mixture for 5 min, sodium t-butoxide (1.05 g, 10.94mmol, 2.5 eq) was added to the resultant solution. The reaction mixturewas stirred for 22 h at 85° C. under nitrogen outside glove box. Themixture was passed through a pad of silica gel, which was rinsed withtoluene. The combined solution was concentrated on a rotary evaporator,followed by flash column chromatography (5% to 10% ethylacetate inhexane, gradient) to afford 2.8 g of a white solid. NMR analysisconfirmed the structure of intermediate compound 18.

Part 2. Synthesis of Intermediate 19

In a nitrogen purged glove box, diamine 18 (1 g, 0.935 mmol) and4-bromo-4′-iodobiphenyl (1.026 g, 2.86 mmol) were dissolved in toluene(30 mL) in a 100 mL of round bottom flask, followed by the addition ofthe toluene (7 mL) solution of tris(dibenzylideneacetone)dipalladium(0)(24 mg, 0.027 eq.) and 1,1′-bis(diphenylphosphino)ferrocene (28 mg,0.053 eq) to the mixture. After stirring the mixture for 5 min, sodiumt-butoxide (229 mg, 2.38 mmol, 2.5 eq) was added to the resultantsolution. The reaction mixture was stirred for 22 h at 95° C. undernitrogen outside glove box. The mixture was passed through a pad ofsilica gel, which was rinsed with toluene. The combined solution wasconcentrated on a rotary evaporator, followed by flash columnchromatography (5% to 20% ethylacetate in hexane, gradiently) to afford1.3 g of a white solid. NMR analysis confirmed the structure of compound19.

Part 3. Synthesis of Compound V

The polymerization of compound 19 was performed as outline in example 1for the synthesis of compound C to yield a white polymer. Molecularweight determination (GPC, THF, polystyrene standards): M_(w)=212,506;M_(n)=73,056; PDI=2.91.

Example 6 Synthesis of Compound W

Compound W was synthesized using the route shown below:

Part 1: Synthesis of Intermediate 21:

In a nitrogen purged glove box, ditriflate 20 (1.7 g, 2.33 mmol) and3-octylaniline (1 g, 4.89 mmol) were dissolved in toluene (20 mL) in a100 mL of round bottom flask, followed by the addition of the toluene(10 mL) solution of tris(dibenzylideneacetone)dipalladium(0) (58 mg,0.027 eq.) and 1,1′-bis(diphenylphosphino)ferrocene (68 mg, 0.053 eq) tothe mixture. After stirring the mixture for 5 min, sodium t-butoxide(0.56 g, 5.82 mmol, 2.5 eq) was added to the resultant solution. Thereaction mixture was stirred for 16 h at 85° C. under nitrogen outsideglove box. The mixture was passed through a pad of silica gel, which wasrinsed with toluene. The combined solution was concentrated on a rotaryevaporator, followed by flash column chromatography (10% to 40%methylene chloride in hexane, gradiently) to afford 1.6 g of product.NMR analysis confirmed the structure of intermediate compound 21.

Part 2: Synthesis of Intermediate 22:

In a nitrogen purged glove box, diamine 21 (1.5 g, 1.78 mmol) and4-bromo-3-iodobenzene (1.51 g, 5.35 mmol) were dissolved in toluene (40mL) in a 100 mL of round bottom flask, followed by the addition of thetoluene (7 mL) solution of tris(dibenzylideneacetone)dipalladium(0) (47mg, 0.027 eq.) and 1,1′-bis(diphenylphosphino)ferrocene (53 mg, 0.053eq) to the mixture. After stirring the mixture for 5 min, sodiumt-butoxide (0.428 g, 4.45 mmol, 2.5 eq) was added to the resultantsolution. The reaction mixture was stirred for 4 days at 90° C. undernitrogen outside glove box. The mixture was passed through a pad ofsilica gel, which was rinsed with toluene. The combined solution wasconcentrated on a rotary evaporator, followed by flash columnchromatography (5% toluene in hexane) to afford 1.6 g of a white solid.NMR analysis confirmed the structure of compound 22.

Part 3. Synthesis of Compound W

The polymerization of compound 22 was performed as outline in example 1for the synthesis of compound C to yield a white polymer in 33% yield.Molecular weight determination (GPC, THF, polystyrene standards):M_(w)=210,638; M_(n)=33,194; PDI=6.34.

Example 7 Synthesis of Compound M

Compound M was synthesized using the route shown below:

Part 1: Synthesis of Intermediate 24:

In a nitrogen purged glove box, ditriflate 23 (3 g, 4.11 mmol) and3-octylaniline (1.77 g, 8.62 mmol) were dissolved in toluene (40 mL) ina 100 mL of round bottom flask, followed by the addition of the toluene(10 mL) solution of tris(dibenzylideneacetone)dipalladium(0) (102 mg,0.027 eq.) and 1,1′-bis(diphenylphosphino)ferrocene (121 mg, 0.053 eq)to the mixture. After stirring the mixture for 5 min, sodium t-butoxide(0.986 g, 10.26 mmol, 2.5 eq) was added to the resultant solution. Thereaction mixture was stirred for 3 days at 85° C. under nitrogen outsideglove box. The mixture was passed through a pad of silica gel, which wasrinsed with toluene. The combined solution was concentrated on a rotaryevaporator, followed by flash column chromatography (5% to 10%ethylacetate in hexane, gradiently) to afford 3 g of a white solid as aproduct. NMR analysis confirmed the structure of intermediate compound24.

Part 2: Synthesis of Intermediate 25:

In a nitrogen purged glove box, diamine 24 (1.2 g, 1.42 mmol) and4-bromo-4′-iodobiphenyl (2.3 g, 6.42 mmol) were dissolved in toluene (30mL) in a 100 mL of round bottom flask, followed by the addition of thetoluene (8 mL) solution of tris(dibenzylideneacetone)dipalladium(0) (35mg, 0.027 eq.) and 1,1′-bis(diphenylphosphino)ferrocene (42 mg, 0.053eq) to the mixture. After stirring the mixture for 5 min, sodiumt-butoxide (341 mg, 3.55 mmol, 2.5 eq) was added to the resultantsolution. The reaction mixture was stirred for 20 h at 95° C. undernitrogen outside glove box. The mixture was passed through a pad ofsilica gel, which was rinsed with toluene. The combined solution wasconcentrated on a rotary evaporator, followed by flash columnchromatography (7% toluene in hexane) to afford 1.2 g of a white solid.NMR analysis confirmed the structure of compound 25.

Part 3. Synthesis of Compound M

The polymerization of compound 25 was performed as outline in example 1for the synthesis of compound C to yield a white polymer. Molecularweight determination (GPC, THF, polystyrene standards): M_(w)=82,023;M_(n)=27,177; PDI=3.02.

Example 8 Synthesis of Compound P

Under an atmosphere of nitrogen bis(1,5-cyclooctadiene)nickel(0) (0.564g, 2.05 mmol), 2,2′-dipyridyl (0.32 g, 2.05 mmol) and 1,5-cyclooctadiene(0.222 g, 2.05 mmol) were dissolved in 2 mL DMF. The catalyst solutionwas stirred and heated in an aluminum block at 60° C. for 30 minutes.The temperature of the heating block was raised to 60° C. Compound 5(1.08 g, 0.85 mmol) and 3,5-dibromostyrene (0.0395 g, 0.15 mmol) weredissolved in toluene (13 mL) and then added to the catalyst solution.The solution was for six hours and then cooled to room temperature. Thepolymer was isolated as previously described for compounds C and T togive compound P as a white polymer in 85% yield (0.825 g). Molecularweight determination (GPC, THF, polystyrene standards): M_(w)=913,631;M_(n)=50,871; PDI=17.96.

Example 9 Synthesis of Compound N

Under an atmosphere of nitrogen bis(1,5-cyclooctadiene)nickel(0) (1.13g, 4.1 mmol), 2,2′-dipyridyl (0.64 g, 4.1 mmol) and 1,5-cyclooctadiene(0.444 g, 4.1 mmol) were dissolved in 3 mL DMF. The catalyst solutionwas stirred and heated in an aluminum block at 60° C. for 30 minutes.The temperature of the heating block was raised to 70° C. Compound 1(0.637 g, 1 mmol) and diamine 26 (0.646 g, 1 mmol) were dissolved intoluene (17 mL) and then added to the catalyst solution. The solutionwas for six hours and then cooled to room temperature. The polymer wasisolated as previously described for compounds C and T to give compoundN as a white polymer in 79% yield (0.760 g). Molecular weightdetermination (GPC, THF, polystyrene standards): M_(w)=284,019;M_(n)=45,611; PDI=6.23.

Example 10 Synthesis of Compound X

Part 1. Synthesis of Compound 28.

In a nitrogen purged glove box, to a 300 ml round bottom flask equippedwith a stir bar was added compound 27 (1.61 g, 1.89 mmol),1-bromo-3-iodobenzene (1.6 g, 5.66 mmol),tris(dibenzylideneacetone)dipalladium(0) (43 mg, 47 μmol),1,1′-bis(diphenyl-phosphino)ferrocene (52 mg, 94 μmol), toluene (50 ml),and sodium-tert-butoxide (0.45 g, 4.7 mmol). The reaction vessel wascapped, removed from glove box, equipped with a reflux condenser and N₂bubbler, and heated at 85° C. for 3 days. The reaction mixture wasallowed to cool to room temperature, diluted with dichloromethane, andfiltered through a plug of silica gel and diatomaceous earth. Thefiltrate was concentrated on a rotary evaporator to give crude product.The crude product was purified by column chromatography (silica gel,hexanes:CH₂Cl₂ gradient) then washed with boiling MeOH to give compound28 as white powder (1.42 g, 65%). ¹H NMR analysis (500 MHz, CD₂Cl₂) isconsistent with structure 28.

Part 2. Synthesis of Compound X.

Compound X was synthesized as previously described for compound C toobtain it as white beads in 65%. Molecular weight determination (GPC,THF, polystyrene standard): M_(w)=320,000; M_(n)=97,000; PDI=3.29.

Example 11 Synthesis of Compound Y1

Part 1. Synthesis of intermediate 29:

In a nitrogen purged glove box, 4-bromo-1-iodobenzene (3.54 g, 12.53mmol) and 4-(p-pentylphenyl)-aniline (3 g, 12.53 mmol) were dissolved intoluene (50 mL) in a 100 mL of round bottom flask, followed by theaddition of the toluene (10 mL) solution oftris(dibenzylideneacetone)dipalladium(0) (286 mg, 0.025 eq.) and1,1′-bis(diphenylphosphino)ferrocene (347 mg, 0.05 equiv) to themixture. After stirring the mixture for 5 min, sodium t-butoxide (1.44g, 15.03 mmol, 1.2 eq) was added to the resultant solution. The reactionmixture was stirred for 6 h at 80° C. under nitrogen outside glove box.The mixture was passed through a pad of silica gel, which was rinsedwith toluene. The combined solution was concentrated on a rotaryevaporator, followed by recrystallization (in hexane and ethylacetatesolvent) and flash column chromatography (5% ethyl acetate in hexane,gradient) to afford 2.3 g of a white solid. NMR analysis confirmed thestructure of intermediate compound 29.

Part 2. Synthesis of Intermediate 31:

To a 100 ml, 2-neck round bottom flask equipped with a stir bar, refluxcondenser, and N₂ bubbler, was added Na₂CO₃ (1.4 g, 13.3 mmol) and water(8 mL). To the Na₂CO₃ solution was added compound 30 (1.65 g, 2.66mmol), compound 29 (2.1 g, 5.3 mmol), Aliquat 336® (0.11 g, 0.27 mmol),toluene (12 ml), and 1,4-dioxane (12 ml). The mixture was sparged withN₂ for 1 h, then bis(di-tert-butyl(4-dimethylaminophenyl)-phosphinedichloropalladium(II) (4.1 mg, 5.3 μmol) was added. The mixture wassparged with N₂ for 10 minutes, then heated at 90° C. for 1.5 h. Thereaction mixture was allowed to cool to RT and diluted with toluene. Theorganic layer was separated, washed with water (3×) and brine, driedover MgSO₄, filtered, concentrated on a rotary evaporator, and driedunder high vacuum to isolate a light brown, foamy solid. The crudeproduct was purified by column chromatography (silica gel, 2:1Hex:CH₂Cl₂) to isolate 2.4 g white, foamy solid in 91%. ¹H NMR (500 MHz,CD₂Cl₂) is consistent with structure 31.

Part 3. Synthesis of Intermediate 32:

In a nitrogen purged glove box, to a 300 mL round bottom flask equippedwith a stir bar was added compound 31 (2.3 g, 2.32 mmol),iodo-bromobiphenyl (2.5 g, 6.9 mmol),tris(dibenzylideneacetone)dipalladium(0) (53 mg, 50 μmol),1,1′-bis(diphenyl-phosphino)ferrocene (64 mg, 120 μmol), toluene (100ml), and sodium-tert-butoxide (0.56 g, 5.8 mmol). The reaction vesselwas capped, removed from glove box, equipped with a reflux condenser andN₂ bubbler, and heated at 95° C. for 18 hours. The reaction mixture wasallowed to cool to RT, diluted with dichloromethane, and filteredthrough a plug of silica gel and diatomaceous earth. The filtrate wasconcentrated on a rotary evaporator to give crude product. The crudeproduct was purified by column chromatography (silica gel,hexanes:CH₂Cl₂ gradient) then washed with boiling MeOH to give 2.8 gwhite powder (83% yield). ¹H NMR analysis (500 MHz, CD₂Cl₂) isconsistent with structure 32.

Part 3. Synthesis of Compound Y1:

The polymerization of compound 32 was performed as outline in example 1for the synthesis of compound C to yield a white polymer in 95% yield.Molecular weight determination (GPC, THF, polystyrene standards):M_(w)=169,000; M_(n)=91,700; PDI=1.84.

Example 12 Synthesis of Compound Y3

Part 1—Synthesis of Intermediate Compound 33:

Under an atmosphere of nitrogen, compound 3 (2.0 g, 3.03 mmol),4-bromo-4′-propylbiphenyl (1.67 g, 6.05 mmol),tris(dibenzylideneacetone)dipalladium(0) (139 mg, 5 mol %),tri-t-butylphosphine (61 mg, 10 mol %) and toluene (27 mL) werecombined. Sodium t-butoxide (0.872 g, 9.08 mmol) was added and thereaction was stirred at room temperature for 40 h.4-bromo-4′-propylbiphenyl (250 mg, 0.091 mmol),tris(dibenzylideneacetone)dipalladium(0) (55 mg, 2 mol %),tri-t-butylphosphine (25 mg, 4 mol %) and sodium t-butoxide (291 mg,3.03 mmol) were then added. After another 23 h, the reaction mixture wasfiltered through a pad of Celite, rinsing with toluene. The solution wasconcentrated on a rotary evaporator and dried under vacuum. The productwas purified by medium pressure liquid chromatography on silica gel(0-40% methylene chloride gradient in hexanes) to give 1.70 g (53%yield) of a white solid. NMR analysis confirmed the structure ofIntermediate Compound 33 as a mixture of 4,4′- and 4,5′-regioisomers.Purity (UPLC): 97.8%.

Part 2—Synthesis of Intermediate 4-bromo-4′-iodobiphenyl:

A 4-neck one liter round bottom flask equipped with mechanical stirrer,thermometer and reflux condenser topped with nitrogen bubbler inlet wascharged with 4-bromobiphenyl (23.31 g, 100 mmol) in acetic acid (400mL), sulfuric acid (10 mL) and water (20 mL). To this stirring mixturewas added iodic acid (4.84 g, 27.5 mmol) followed immediately byaddition of iodine chips (11.17 g, 44.0 mmol). The reaction flask wasimmersed in a preheated tri(ethylene glycol) heating bath and heated at65° C. internal temperature. After 30 min the bath temperature wasincreased such that the internal temperature raised to 85° C. after 20min. Heating at this temperature was continued for 4.5 hours at whichpoint UPLC analysis showed the reaction to be complete. After stirringovernight at room temperature the reaction mixture was vacuum filteredthrough a coarse fritted funnel and the solids were rinsed with water.The resulting white solid (32.1 g, 89% yield) had mp 177-179° C. and wasused without further purification in the next step. NMR analysisconfirmed the structure of Intermediate Compound3,4-bromo-4′-iodobiphenyl. Purity (UPLC): >99%.

Part 3—Synthesis of Intermediate Compound 34:

In a nitrogen purged glovebox, a 3-neck round bottom flask equipped witha magnetic stirrer, thermometer and reflux condenser topped with a gasinlet adaptor in the closed position was charged with 33 (1.70 g, 1.62mmol), 4-bromo-4′-iodobiphenyl (2.62 g, 7.29 mmol),tris(dibenzylideneacetone)dipalladium(0) (178 mg, 12 mol %),bis(diphenylphosphinoferrocene) (215 mg, 24 mol %) and toluene (30 mL)through the open neck. Sodium t-butoxide (0.342 g, 3.56 mmol) was added,the open neck was capped and the reaction vessel was removed from theglovebox. A nitrogen bubbler hose was fitted to the gas inlet adaptorand the stopcock was turned to the open position under a slight positivepressure of nitrogen. The reaction on was heated reflux with atri(ethylene glycol) bath. After 16 h, the reaction was cooled to roomtemperature and tris(dibenzylideneacetone)dipalladium(0) (178 mg, 12 mol%), bis(diphenylphosphino)ferrocene (215 mg, 24 mol %) and sodiumt-butoxide (342 mg, 3.56 mmol) was added to the reaction mixture. Afteradditional 2 h at reflux, the reaction mixture was cooled to roomtemperature. After 72 h at room temperature the reaction mixture wasfiltered through a pad of Celite, rinsing with toluene. The filtrate wasconcentrated by rotary evaporation. The crude product was dried underhigh vacuum and purified by medium pressure liquid chromatography onsilica gel (0-35% methylene chloride gradient in hexanes) to give 1.42 g(58% yield) of a white solid. NMR analysis confirmed the structure ofIntermediate Compound 34 as a mixture of 4,4′- and 4,5′-regioisomers.Purity (UPLC): 98.7%.

Part 4—Synthesis of Compound Y3.

The polymerization of compound 34 was performed as outline in example 1for the synthesis of compound C to yield a white polymer. Molecularweight determination (GPC, THF, polystyrene standards): M_(w)=512,983;M_(n)=136,936; PDI=3.75.

DEVICE EXAMPLES

The following materials were used:

Buffer 1 is an aqueous dispersion of polypyrrole and a polymericfluorinated sulfonic acid. The material was prepared using a proceduresimilar to that described in Example 1 of published U.S. patentapplication no. 2005/0205860.

H1:

E1:

-   Alq3=tris(8-hydroxyquinoline)aluminum-   ZrQ=tetrakis-(8-hydroxyquinoline) zirconium

Device Example 1

This example demonstrates the fabrication and performance of a devicehaving deep blue emission.

The device had the following layers:

anode=Indium Tin Oxide (ITO): 50 nm

buffer layer=Buffer 1 (25 nm)

hole transport layer=Compound C, from Example 1 (20 nm)

photoactive layer=13:1 host H1:dopant E1 (47 nm)

electron transport layer=ZrQ (20 nm)

cathode=CsF/Al (0.7/100 nm)

OLED devices were fabricated by a combination of solution processing andthermal evaporation techniques. Patterned indium tin oxide (ITO) coatedglass substrates from Thin Film Devices, Inc were used. These ITOsubstrates are based on Corning 1737 glass coated with ITO having asheet resistance of 50 ohms/square and 80% light transmission. Thepatterned ITO substrates were cleaned ultrasonically in aqueousdetergent solution and rinsed with distilled water. The patterned ITOwas subsequently cleaned ultrasonically in acetone, rinsed withisopropanol, and dried in a stream of nitrogen.

Immediately before device fabrication the cleaned, patterned ITOsubstrates were treated with UV ozone for 10 minutes. Immediately aftercooling, an aqueous dispersion of Buffer 1 was spin-coated over the ITOsurface and heated to remove solvent. After cooling, the substrates werethen spin-coated with a solution of the hole transport material, andthen heated to remove solvent. After cooling, the substrates werespin-coated with the emissive layer solution, and heated to removesolvent. The substrates were masked and placed in a vacuum chamber. AZrQ layer was deposited by thermal evaporation, followed by a layer ofCsF. Masks were then changed in vacuo and a layer of Al was deposited bythermal evaporation. The chamber was vented, and the devices wereencapsulated using a glass lid, desiccant, and UV curable epoxy.

The OLED samples were characterized by measuring their (1)current-voltage (1-V) curves, (2) electroluminescence radiance versusvoltage, and (3) electroluminescence spectra versus voltage. All threemeasurements were performed at the same time and controlled by acomputer. The current efficiency of the device at a certain voltage isdetermined by dividing the electroluminescence radiance of the LED bythe current density needed to run the device. The unit is a cd/A. Thepower efficiency is the current efficiency divided by the operatingvoltage. The unit is lm/W. The results are given in Table 1, below.

Device Example 2

This example demonstrates the fabrication and performance of a devicehaving deep blue emission. The following materials were used:

Indium Tin Oxide (ITO): 50 nm

buffer layer=Buffer 1 (25 nm)

hole transport layer=Compound C (20 nm)

photoactive layer=4:1 host H1:dopant E1 (39 nm)

electron transport layer=ZrQ (20 nm)

cathode=CsF/Al (0.8/100 nm)

OLED devices were fabricated by a combination of solution processing andthermal evaporation techniques. Patterned indium tin oxide (ITO) coatedglass substrates from Thin Film Devices, Inc were used. These ITOsubstrates are based on Corning 1737 glass coated with ITO having asheet resistance of 50 ohms/square and 80% light transmission. Thepatterned ITO substrates were cleaned ultrasonically in aqueousdetergent solution and rinsed with distilled water. The patterned ITOwas subsequently cleaned ultrasonically in acetone, rinsed withisopropanol, and dried in a stream of nitrogen.

Immediately before device fabrication the cleaned, patterned ITOsubstrates were treated with UV ozone for 10 minutes. Immediately aftercooling, an aqueous dispersion of Buffer 1 was spin-coated over the ITOsurface and heated to remove solvent. After cooling, the substrates werethen spin-coated with a solution of the hole transport material, andthen heated to remove solvent. After cooling, the substrates were maskedand loaded into the vacuum chamber. A 4:1 ratio of fluorescenthost:dopant was co-evaporated to a thickness of 39 nm. The substrateswere masked and placed in a vacuum chamber. A ZrQ layer was deposited bythermal evaporation, followed by a layer of CsF. Masks were then changedin vacuo and a layer of Al was deposited by thermal evaporation. Thechamber was vented, and the devices were encapsulated using a glass lid,dessicant, and UV curable epoxy.

The OLED samples were characterized as described above. The results aregiven in Table 1 below.

Device Example 3

This example demonstrates the fabrication and performance of a devicehaving deep blue emission. The following materials were used:

Indium Tin Oxide (ITO): 50 nm

buffer layer=Buffer 1 (50 nm)

hole transport layer=Compound T (20 nm)

photoactive layer=6:1 host H1:dopant E1 (32 nm)

electron transport layer=ZrQ (10 nm)

cathode=CsF/Al (0.7/100 nm)

OLED devices were fabricated by a combination of solution processing andthermal evaporation techniques. Patterned indium tin oxide (ITO) coatedglass substrates from Thin Film Devices, Inc were used. These ITOsubstrates are based on Corning 1737 glass coated with ITO having asheet resistance of 50 ohms/square and 80% light transmission. Thepatterned ITO substrates were cleaned ultrasonically in aqueousdetergent solution and rinsed with distilled water. The patterned ITOwas subsequently cleaned ultrasonically in acetone, rinsed withisopropanol, and dried in a stream of nitrogen.

Immediately before device fabrication the cleaned, patterned ITOsubstrates were treated with UV ozone for 10 minutes. Immediately aftercooling, an aqueous dispersion of Buffer 1 was spin-coated over the ITOsurface and heated to remove solvent. After cooling, the substrates werethen spin-coated with a solution of the hole transport material, andthen heated to remove solvent. After cooling, the substrates were maskedand loaded into the vacuum chamber. A 6:1 ratio of fluorescenthost:dopant was co-evaporated to a thickness of 32 nm. The substrateswere masked and placed in a vacuum chamber. A ZrQ layer was deposited bythermal evaporation, followed by a layer of CsF. Masks were then changedin vacuo and a layer of Al was deposited by thermal evaporation. Thechamber was vented, and the devices were encapsulated using a glass lid,dessicant, and UV curable epoxy.

The OLED samples were characterized as described above. The results aregiven in Table 1 below.

Device Example 4

This example demonstrates the fabrication and performance of a devicehaving deep blue emission.

The device had the following layers:

anode=Indium Tin Oxide (ITO): 50 nm

buffer layer=Buffer 1 (25 nm)

hole transport layer=Compound V

photoactive layer=13:1 host H1:dopant E1 (47 nm)

electron transport layer=ZrQ (20 nm)

cathode=CsF/Al (0.7/100 nm)

OLED devices were fabricated by a combination of solution processing andthermal evaporation techniques. Patterned indium tin oxide (ITO) coatedglass substrates from Thin Film Devices, Inc were used. These ITOsubstrates are based on Corning 1737 glass coated with ITO having asheet resistance of 50 ohms/square and 80% light transmission. Thepatterned ITO substrates were cleaned ultrasonically in aqueousdetergent solution and rinsed with distilled water. The patterned ITOwas subsequently cleaned ultrasonically in acetone, rinsed withisopropanol, and dried in a stream of nitrogen.

Immediately before device fabrication the cleaned, patterned ITOsubstrates were treated with UV ozone for 10 minutes. Immediately aftercooling, an aqueous dispersion of Buffer 1 was spin-coated over the ITOsurface and heated to remove solvent. After cooling, the substrates werethen spin-coated with a solution of the hole transport material, andthen heated to remove solvent. After cooling, the substrates werespin-coated with the emissive layer solution, and heated to removesolvent. The substrates were masked and placed in a vacuum chamber. AZrQ layer was deposited by thermal evaporation, followed by a layer ofCsF.

Masks were then changed in vacuo and a layer of Al was deposited bythermal evaporation. The chamber was vented, and the devices wereencapsulated using a glass lid, desiccant, and UV curable epoxy.

The OLED samples were characterized by measuring their (1)current-voltage (1-V) curves, (2) electroluminescence radiance versusvoltage, and (3) electroluminescence spectra versus voltage. All threemeasurements were performed at the same time and controlled by acomputer. The current efficiency of the device at a certain voltage isdetermined by dividing the electroluminescence radiance of the LED bythe current density needed to run the device. The unit is a cd/A. Thepower efficiency is the current efficiency divided by the operatingvoltage. The unit is lm/W. The results are given in Table 1, below.

Device Example 5

This example demonstrates the fabrication and performance of a devicehaving deep blue emission. The following materials were used:

Indium Tin Oxide (ITO): 50 nm

buffer layer=Buffer 1 (25 nm)

hole transport layer=Compound V (20 nm)

photoactive layer=4:1 host H1:dopant E1 (39 nm)

electron transport layer=ZrQ (20 nm)

cathode=CsF/Al (0.8/100 nm)

OLED devices were fabricated by a combination of solution processing andthermal evaporation techniques. Patterned indium tin oxide (ITO) coatedglass substrates from Thin Film Devices, Inc were used. These ITOsubstrates are based on Corning 1737 glass coated with ITO having asheet resistance of 50 ohms/square and 80% light transmission. Thepatterned ITO substrates were cleaned ultrasonically in aqueousdetergent solution and rinsed with distilled water. The patterned ITOwas subsequently cleaned ultrasonically in acetone, rinsed withisopropanol, and dried in a stream of nitrogen.

Immediately before device fabrication the cleaned, patterned ITOsubstrates were treated with UV ozone for 10 minutes. Immediately aftercooling, an aqueous dispersion of Buffer 1 was spin-coated over the ITOsurface and heated to remove solvent. After cooling, the substrates werethen spin-coated with a solution of the hole transport material, andthen heated to remove solvent. After cooling, the substrates were maskedand loaded into the vacuum chamber. A 4:1 ratio of fluorescenthost:dopant was co-evaporated to a thickness of 39 nm. The substrateswere masked and placed in a vacuum chamber. A ZrQ layer was deposited bythermal evaporation, followed by a layer of CsF. Masks were then changedin vacuo and a layer of Al was deposited by thermal evaporation. Thechamber was vented, and the devices were encapsulated using a glass lid,dessicant, and UV curable epoxy.

The OLED samples were characterized as described above. The results aregiven in Table 1 below.

Device Example 6

This example demonstrates the fabrication and performance of a devicehaving deep blue emission. The following materials were used:

Indium Tin Oxide (ITO): 50 nm

buffer layer=Buffer 1 (25 nm)

hole transport layer=Compound Z2 (20 nm)

photoactive layer=4:1 host H1:dopant E1 (39 nm)

electron transport layer=ZrQ (20 nm)

cathode=CsF/Al (0.8/100 nm)

OLED devices were fabricated by a combination of solution processing andthermal evaporation techniques. Patterned indium tin oxide (ITO) coatedglass substrates from Thin Film Devices, Inc were used. These ITOsubstrates are based on Corning 1737 glass coated with ITO having asheet resistance of 50 ohms/square and 80% light transmission. Thepatterned ITO substrates were cleaned ultrasonically in aqueousdetergent solution and rinsed with distilled water. The patterned ITOwas subsequently cleaned ultrasonically in acetone, rinsed withisopropanol, and dried in a stream of nitrogen.

Immediately before device fabrication the cleaned, patterned ITOsubstrates were treated with UV ozone for 10 minutes. Immediately aftercooling, an aqueous dispersion of Buffer 1 was spin-coated over the ITOsurface and heated to remove solvent. After cooling, the substrates werethen spin-coated with a solution of the hole transport material, andthen heated to remove solvent. After cooling, the substrates were maskedand loaded into the vacuum chamber. A 4:1 ratio of fluorescenthost:dopant was co-evaporated to a thickness of 39 nm. The substrateswere masked and placed in a vacuum chamber. A ZrQ layer was deposited bythermal evaporation, followed by a layer of CsF. Masks were then changedin vacuo and a layer of Al was deposited by thermal evaporation. Thechamber was vented, and the devices were encapsulated using a glass lid,dessicant, and UV curable epoxy.

The OLED samples were characterized as described above. The results aregiven in Table 1 below.

Device Example 7

This example demonstrates the fabrication and performance of a devicehaving deep blue emission.

The device had the following layers:

anode=Indium Tin Oxide (ITO): 50 nm

buffer layer=Buffer 1 (25 nm)

hole transport layer=Compound Z3

photoactive layer=13:1 host H1:dopant E1 (47 nm)

electron transport layer=ZrQ (20 nm)

cathode=CsF/Al (0.7/100 nm)

OLED devices were fabricated by a combination of solution processing andthermal evaporation techniques. Patterned indium tin oxide (ITO) coatedglass substrates from Thin Film Devices, Inc were used. These ITOsubstrates are based on Corning 1737 glass coated with ITO having asheet resistance of 50 ohms/square and 80% light transmission. Thepatterned ITO substrates were cleaned ultrasonically in aqueousdetergent solution and rinsed with distilled water. The patterned ITOwas subsequently cleaned ultrasonically in acetone, rinsed withisopropanol, and dried in a stream of nitrogen.

Immediately before device fabrication the cleaned, patterned ITOsubstrates were treated with UV ozone for 10 minutes. Immediately aftercooling, an aqueous dispersion of Buffer 1 was spin-coated over the ITOsurface and heated to remove solvent. After cooling, the substrates werethen spin-coated with a solution of the hole transport material, andthen heated to remove solvent. After cooling, the substrates werespin-coated with the emissive layer solution, and heated to removesolvent. The substrates were masked and placed in a vacuum chamber. AZrQ layer was deposited by thermal evaporation, followed by a layer ofCsF. Masks were then changed in vacuo and a layer of Al was deposited bythermal evaporation. The chamber was vented, and the devices wereencapsulated using a glass lid, desiccant, and UV curable epoxy.

The OLED samples were characterized by measuring their (1)current-voltage (I-V) curves, (2) electroluminescence radiance versusvoltage, and (3) electroluminescence spectra versus voltage. All threemeasurements were performed at the same time and controlled by acomputer. The current efficiency of the device at a certain voltage isdetermined by dividing the electroluminescence radiance of the LED bythe current density needed to run the device. The unit is a cd/A. Thepower efficiency is the current efficiency divided by the operatingvoltage. The unit is lm/W. The results are given in Table 1, below.

Device Example 8

This example demonstrates the fabrication and performance of a devicehaving deep blue emission. The following materials were used:

Indium Tin Oxide (ITO): 50 nm

buffer layer=Buffer 1 (25 nm)

hole transport layer=Compound Z3 (20 nm)

photoactive layer=4:1 host H1:dopant E1 (39 nm)

electron transport layer=ZrQ (20 nm)

cathode=CsF/Al (0.8/100 nm)

OLED devices were fabricated by a combination of solution processing andthermal evaporation techniques. Patterned indium tin oxide (ITO) coatedglass substrates from Thin Film Devices, Inc were used. These ITOsubstrates are based on Corning 1737 glass coated with ITO having asheet resistance of 50 ohms/square and 80% light transmission. Thepatterned ITO substrates were cleaned ultrasonically in aqueousdetergent solution and rinsed with distilled water. The patterned ITOwas subsequently cleaned ultrasonically in acetone, rinsed withisopropanol, and dried in a stream of nitrogen.

Immediately before device fabrication the cleaned, patterned ITOsubstrates were treated with UV ozone for 10 minutes. Immediately aftercooling, an aqueous dispersion of Buffer 1 was spin-coated over the ITOsurface and heated to remove solvent. After cooling, the substrates werethen spin-coated with a solution of the hole transport material, andthen heated to remove solvent. After cooling, the substrates were maskedand loaded into the vacuum chamber. A 4:1 ratio of fluorescenthost:dopant was co-evaporated to a thickness of 39 nm. The substrateswere masked and placed in a vacuum chamber. A ZrQ layer was deposited bythermal evaporation, followed by a layer of CsF. Masks were then changedin vacuo and a layer of Al was deposited by thermal evaporation. Thechamber was vented, and the devices were encapsulated using a glass lid,dessicant, and UV curable epoxy.

The OLED samples were characterized as described above. The results aregiven in Table 1 below.

TABLE 1 EL CE Voltage peak Example [cd/A] [V] [nm] CIE [x] CIE [y]Device 1 6.28 5.0 462 0.138 0.135 Device 2 8.53 4.4 462 0.136 0.136Device 3 8.1 4.0 458 0.138 0.107 Device 4 6.26 5.3 458 0.140 0.121Device 5 8.85 4.1 462 0.137 0.126 Device 6 7.85 4.4 462 0.137 0.129Device 7 6.49 5.0 460 0.138 0.127 Device 8 7.96 4.5 462 0.137 0.131 Alldata @ 1000 nits, CE = current efficiency, CIE[x] and CIE[y] refer tothe x and y color coordinates according to the C.I.E. chromaticity scale(Commission Internationale de L'Eclairage, 1931).

Note that not all of the activities described above in the generaldescription or the examples are required, that a portion of a specificactivity may not be required, and that one or more further activitiesmay be performed in addition to those described. Still further, theorder in which activities are listed are not necessarily the order inwhich they are performed.

In the foregoing specification, the concepts have been described withreference to specific embodiments. However, one of ordinary skill in theart appreciates that various modifications and changes can be madewithout departing from the scope of the invention as set forth in theclaims below. Accordingly, the specification and figures are to beregarded in an illustrative rather than a restrictive sense, and allsuch modifications are intended to be included within the scope ofinvention.

Benefits, other advantages, and solutions to problems have beendescribed above with regard to specific embodiments. However, thebenefits, advantages, solutions to problems, and any feature(s) that maycause any benefit, advantage, or solution to occur or become morepronounced are not to be construed as a critical, required, or essentialfeature of any or all the claims.

It is to be appreciated that certain features are, for clarity,described herein in the context of separate embodiments, may also beprovided in combination in a single embodiment. Conversely, variousfeatures that are, for brevity, described in the context of a singleembodiment, may also be provided separately or in any subcombination.The use of numerical values in the various ranges specified herein isstated as approximations as though the minimum and maximum values withinthe stated ranges were both being preceded by the word “about.” In thismanner, slight variations above and below the stated ranges can be usedto achieve substantially the same results as values within the ranges.Also, the disclosure of these ranges is intended as a continuous rangeincluding every value between the minimum and maximum average valuesincluding fractional values that can result when some of components ofone value are mixed with those of different value. Moreover, whenbroader and narrower ranges are disclosed, it is within thecontemplation of this invention to match a minimum value from one rangewith a maximum value from another range and vice versa.

What is claimed is:
 1. A compound having Formula I, Formula II, orFormula III:

wherein: Ar¹ is the same or different at each occurrence and is selectedfrom the group consisting of phenylene, substituted phenylene,naphthylene, and substituted naphthylene; Ar² is the same or differentat each occurrence and is an aryl group; M is the same or different ateach occurrence and is a conjugated moiety; T¹ and T² are independentlythe same or different at each occurrence and are conjugated moietieswhich are connected in a non-planar configuration; a is the same ordifferent at each occurrence and is an integer from 1 to 6; b, c, and dare mole fractions such that b+c+d=1.0, with the proviso that c is notzero, and at least one of b and d is not zero, and when b is zero, Mcomprises at least two triarylamine units; e is the same or different ateach occurrence and is an integer from 1 to 6; and n is an integergreater than 1; with the proviso that when [T¹-T²] in Formula (I) is adinaphthylene group Ar2 does not contain an alkyl substituents.
 2. Thecompound of claim 1, wherein the members of [T¹-T²] are independentlyselected from the group consisting of:

where: R is the same or different and is selected from the groupconsisting of alkyl, aryl, alkoxy, aryloxy, fluoroalkyl, fluoroaryl,fluoroaryloxy fluoroalkyloxy, oxyalkyl, and alkenyl groups.
 3. Thecompound of claim 2, wherein R is selected from the group consisting ofC1-10 alkyl and C1-10 alkoxy.
 4. The compound of claim 2, wherein R isselected from the group consisting of C3-8 branched alkyl and C3-8branched alkoxy.
 5. The compound of claim 2, wherein both R groups arejoined together to form a non-aromatic ring.
 6. The compound of claim 1,wherein a is 1-3.
 7. The compound of claim 1, wherein Ar² has Formula a

where: R¹ is the same or different at each occurrence and is selectedfrom the group consisting of alkyl, alkoxy, and silyl; f is the same ordifferent at each occurrence and is an integer from 0-4; g is an integerfrom 0-5; and m is an integer from 1 to
 5. 8. The compound of claim 1,wherein Ar² is selected from the group consisting phenyl, p-biphenyl,p-terphenyl, naphthyl, phenylnaphthyl, and naphthylphenyl.
 9. Thecompound of claim 1, wherein Ar² has a substituent comprising acrosslinking group.
 10. The compound of claim 1, wherein at least oneAr² has at least one substituent selected from the group consisting ofalkyl, alkoxy and silyl.
 11. The compound of claim 1 having Formula III,wherein c is at least 0.4.
 12. The compound of claim 11, wherein M isselected from the group consisting of triarylamine units and an aromaticunit having a crosslinkable substituent.
 13. A compound selected fromthe group consisting of Compound A:

and Compound B:


14. A compound selected from the group consisting of Compound C

Compound D:

Compound E:

Compound F:

Compound G:

Compound H:

Compound I:

Compound J:

Compound K:

Compound L:

Compound M:

and Compound M1:


15. A compound selected from the group consisting of Compound N:

Compound O:

Compound P:

Compound Q:

Compound R:

Compound S:

Compound T:

Compound U:

Compound V:

Compound W:

Compound X:

and Compounds Y1-Y4


16. An organic electronic device comprising a first electrical contactlayer, a second electrical contact layer and an active layertherebetween, wherein the active layer comprises a compound havingFormula I, Formula II, or Formula III:

wherein: Ar¹ is the same or different at each occurrence and is selectedfrom the group consisting of phenylene, substituted phenylene,naphthylene, and substituted naphthylene; Ar² is the same or differentat each occurrence and is an aryl group; M is the same or different ateach occurrence and is a conjugated moiety; T¹ and T² are independentlythe same or different at each occurrence and are conjugated moietieswhich are connected in a non-planar configuration; a is the same ordifferent at each occurrence and is an integer from 1 to 6; b, c, and dare mole fractions such that b+c+d=1.0, with the proviso that c is notzero, and at least one of b and d is not zero, and when b is zero, Mcomprises at least two triarylamine units; e is the same or different ateach occurrence and is an integer from 1 to 6; and n is an integergreater than 1; with the proviso that when [T¹-T²] in Formula (I) is adinaphthylene group Ar2 does not contain an alkyl substituents.
 17. Thedevice of claim 16, wherein the active layer is a hole transport layer.18. The device of claim 17, wherein the hole transport layer consistsessentially of the Compound having Formula I, Formula II, or FormulaIII.
 19. The device of claim 16, wherein the active layer is aphotoactive layer.
 20. The device of claim 19, wherein the active layerfurther comprises a photoactive material.
 21. The device of claim 20,wherein the active layer consists essentially of a photoactive materialand a compound having Formula I, Formula II, or Formula III.
 22. Thecompound of claim 1, wherein at least one Ar¹ is a substituted phenylwith a substituent selected from the group consisting of alkyl, alkoxy,silyl, and a substitutent with a crosslinking group.